U.S. patent number 7,061,081 [Application Number 10/220,846] was granted by the patent office on 2006-06-13 for resin composition, heat-resistant resin paste and semiconductor device using them and method for manufacture thereof.
This patent grant is currently assigned to Hitachi Chemical Co., Ltd.. Invention is credited to Aizou Kaneda, Hidekazu Matsuura, Yoshii Morishita, Hiroshi Nishizawa, Yoshihiro Nomura, Touichi Sakata, Toshiaki Tanaka, Yasuhiro Yano, Masaaki Yasuda.
United States Patent |
7,061,081 |
Yano , et al. |
June 13, 2006 |
Resin composition, heat-resistant resin paste and semiconductor
device using them and method for manufacture thereof
Abstract
There are disclosed a resin composition comprising (A) a
heat-resistant resin soluble in a solvent at room temperature, (B)
a heat-resistant resin which is insoluble in a solvent at room
temperature but becomes soluble by heating, and (C) a solvent; a
heat-resistant resin paste further containing (D) particles or
liquid state material D showing rubber elasticity; and a
semiconductor device using the same and a method for producing the
same.
Inventors: |
Yano; Yasuhiro (Ichihara,
JP), Matsuura; Hidekazu (Ichihara, JP),
Nomura; Yoshihiro (Ichihara, JP), Morishita;
Yoshii (Hitachi, JP), Sakata; Touichi
(Hitachinaka, JP), Nishizawa; Hiroshi (Kitaibaraki,
JP), Tanaka; Toshiaki (Tsukuba, JP),
Yasuda; Masaaki (Tsukuba, JP), Kaneda; Aizou
(Yokohama, JP) |
Assignee: |
Hitachi Chemical Co., Ltd.
(Tokyo, JP)
|
Family
ID: |
27554737 |
Appl.
No.: |
10/220,846 |
Filed: |
March 6, 2001 |
PCT
Filed: |
March 06, 2001 |
PCT No.: |
PCT/JP01/01714 |
371(c)(1),(2),(4) Date: |
September 06, 2002 |
PCT
Pub. No.: |
WO01/66645 |
PCT
Pub. Date: |
September 13, 2001 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20030082925 A1 |
May 1, 2003 |
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Foreign Application Priority Data
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Mar 6, 2000 [JP] |
|
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2000-065718 |
Mar 9, 2000 [JP] |
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2000-070975 |
Mar 9, 2000 [JP] |
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2000-071023 |
Mar 9, 2000 [JP] |
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2000-071024 |
Mar 9, 2000 [JP] |
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2000-071025 |
Jul 26, 2000 [JP] |
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2000-224762 |
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Current U.S.
Class: |
257/678; 524/233;
524/210; 524/138; 524/107; 324/251; 324/538; 324/378; 524/104;
524/115; 524/173; 257/E23.167; 257/E21.576; 257/E21.261;
257/E21.259 |
Current CPC
Class: |
H01L
21/02282 (20130101); H01L 21/02118 (20130101); H01L
21/3122 (20130101); H01L 21/312 (20130101); H01L
21/02216 (20130101); H01L 21/02126 (20130101); G03F
7/0387 (20130101); H01L 23/5329 (20130101); H01L
2924/0002 (20130101); H01L 2924/0002 (20130101); H01L
2924/00 (20130101) |
Current International
Class: |
C08L
79/08 (20060101); H01L 23/48 (20060101) |
Field of
Search: |
;524/111,115,173,104,205,210,378,538,514,386,356,361,345,138,233,251,107
;426/99 ;214/13 ;257/678 |
References Cited
[Referenced By]
U.S. Patent Documents
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|
|
5037862 |
August 1991 |
Nishizawa et al. |
5087658 |
February 1992 |
Nishizawa et al. |
5164816 |
November 1992 |
Nishizawa et al. |
5374677 |
December 1994 |
Nishio et al. |
|
Foreign Patent Documents
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3287668 |
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Dec 1991 |
|
JP |
|
4285660 |
|
Oct 1992 |
|
JP |
|
4285662 |
|
Oct 1992 |
|
JP |
|
Primary Examiner: Woodward; Ana
Attorney, Agent or Firm: Antonelli, Terry, Stout and Kraus,
LLP.
Claims
The invention claimed is:
1. A heat-resistant paste which comprises: (A) an aromatic
thermoplastic resin soluble in a polar solvent (C) at room
temperature, (B) an aromatic thermoplastic resin which is insoluble
in the polar solvent (C) at room temperature but is soluble by
heating, (C) the polar solvent (C) wherein the polar solvent (C) is
selected from the group consisting of a protonic solvent,
acetonitrile, dimethoxyethane, dimethylformamide,
dimethylsulfoxide, hexamethylphosphoric acid triamide,
N-methyl-2-pyrrolidone, dimethylacetamide, .gamma.-butyrolactone
and an ether solvent, and (D) a rubber elastomer.
2. The heat-resistant resin paste according to claim 1, wherein the
surface of the rubber elastomer is modified by an epoxy group.
3. The heat-resistant resin paste according to claim 2, wherein the
average particle size of the rubber elastomer is 0.1 to 50
.mu.m.
4. The heat-resistant resin paste according to claim 3, wherein the
modulus of elasticity at 25.degree. C. of a resin film obtained
from the heat-resistant resin paste can be optionally controlled in
the range of 0.2 to 3.0 GPa and the modulus of elasticity at
150.degree. C. of a resin film obtained from the heat-resistant
resin paste is within the range of 10 to 100% to a modulus of
elasticity at -65.degree. C.
5. The heat-resistant resin paste according to claim 4, wherein the
glass transition temperature (Tg) of a resin film obtained from the
heat-resistant resin paste is 180.degree. C. or higher and the
thermal decomposition temperature is 300.degree. C. or higher.
6. The heat-resistant resin paste according to claim 5, wherein the
viscosity of the heat-resistant resin paste is within the range of
1 to 1000 Pas, a thixotropic coefficient of the heat-resistant
resin paste is 1.2 or more and the composition is capable of
forming a fine pattern.
7. A semiconductor device which comprises using the heat-resistant
resin paste according to claim 6.
8. The heat-resistant resin paste according to claim 1, wherein the
average particle size of the rubber elastomer is 0.1 to 50
.mu.m.
9. The heat-resistant paste according to claim 1, wherein the polar
solvent (C) is at least one solvent selected from the group
consisting of alcohol, a carboxylic acid, acetonitrile,
dimethoxyethane, dimethylformamide (DMF), dimethylsulfoxide (DMSO),
hexamethyl phosphoric acid triamide (HMPA), N-methyl-2-pyrrolidone
(NMP), dimethylacetamide (DMAc), .gamma.-butyrolactone, diethylene
glycol dimethyl ether, diethylene gylcol diethyl ether, diethylene
glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene
glycol dimethyl ether, triethylene glycol diethyl ether,
triethylene glycol dipropyl ether, triethylene glycol dibutyl
ether, tetraethylene glycol dimethyl ether, tetraethylene glycol
diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene
glycol dibutyl ether, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, diethylene glycol dimethyl
ether, triethylene glycol dimethyl ether, triethylene glycol
monomethyl ether, triethylene glycol monoethyl ether, tetraethylene
glycol monomethyl ether, and tetraethylene glycol monoethyl
ether.
10. A heat-resistant resin paste which comprises: (A'') a
heat-resistant resin A'' soluble in a solvent (C'') at room
temperature and a temperature at a time of drying while heating,
(B'') a heat-resistant resin B'' which is insoluble in the solvent
(C'') at room temperature but is soluble at a temperature at the
time of drying while heating, (C'') the solvent, and (D'')
particles or a liquid state material D each showing rubber
elasticity, wherein the heat-resistant resin A'' of (A'') and the
heat-resistant resin B'' of (B'') are aromatic polyimide resins
obtained by aromatic tetracarboxylic acid dianhydride and aromatic
diamine, and a main component of the particles showing rubber
elasticity of (D) is silicone rubber.
11. The heat-resistant resin paste according to claim 10, wherein
the heat-resistant resin B'' of (B'') is an aromatic polyimide
resin obtained by reacting an aromatic tetracarboxylic acid
dianhydride containing 50 mol% or more of
3,4,3',4'-benzophenonetetracarboxylic acid dianhydride and an
aromatic diamine containing 50 mol% or more of 4,4'-diaminodiphenyl
ether, and a main solvent of (C'') is .gamma.-butyrolactone.
12. The heat-resistant resin paste according to claim 11, wherein
the average particle size of the particles showing rubber
elasticity is 0.1 to 50 .mu.m.
13. The heat-resistant resin paste according to claim 12, wherein
the modulus of elasticity of a resin film obtained from the
heat-resistant resin paste at 25.degree. C. can be optionally
controlled in the range of 0.2 to 3.0 GPa and a modulus of
elasticity at 150.degree. C. is within the range of 10 to 100% to a
modulus of elasticity at -65.degree. C.
14. The heat-resistant resin paste according to claim 13, wherein
the glass transition temperature (Tg) of a resin film obtained from
the heat-resistant resin paste is 180.degree. C. or 20 higher and a
5% weight loss temperature is 300.degree. C. or higher.
15. The heat-resistant resin paste according to claim 14, wherein
the viscosity of the heat-resistant resin paste is within the range
of 10 to 1000 Pas, and the thixotropic coefficient of the
heat-resistant resin paste is 1.2 or more.
16. A semiconductor device which comprises a resin film obtained
from a heat-resistant resin paste according to claim 15.
17. The heat-resistant resin paste according to claim 10, wherein
the heat-resistant resin B'' of (B'') is an aromatic polyimide
resin obtained by reacting an aromatic tetracarboxylic acid
dianhydride containing 50 mol% or more of
3,4,3'',4''-benzophenonetetracarboxylic acid dianhydride and an
aromatic diamine containing 50 mol% or more of
4,4''-diaminodiphenyl ether, and a main solvent of (C'') is
.gamma.-butyrolactone.
18. The heat-resistant resin paste according to claim 10, wherein
the average particle size of the particles showing rubber
elasticity is 0.1 to 50 .mu.m.
19. The heat-resistant resin paste according to claim 10, wherein
the modulus of elasticity of a resin film obtained from the
heat-resistant resin paste at 25.degree. C. can be optionally
controlled in the range of 0.2 to 3.0 GPa and the modulus of
elasticity at 150.degree. C. is within the range of 10 to 100% to a
modulus of elasticity at -65.degree. C.
20. The heat-resistant resin paste according to claim 10, wherein
the glass transition temperature (Tg) of a resin film obtained from
the heat-resistant resin paste is 180.degree. C. or higher and a 5%
weight loss temperature is 300.degree. C. or higher.
21. The heat-resistant resin paste according to claim 10, wherein
the viscosity of the heat-resistant resin paste is within the range
of 10 to 1000 Pas, and the thixotropic coefficient of the
heat-resistant resin paste is 1.2 or more.
22. A semiconductor device which comprises a resin film obtained
from a heat-resistant resin paste according to claim 10.
23. A heat-resistant paste which comprises: (A'') a heat-resistant
resin A'' soluble in a solvent (C'') at room temperature and a
temperature at a time of drying while heating, (B'') a
heat-resistant resin B'' which is insoluble in the solvent (C'') at
room temperature but is soluble at a temperature at the time of
drying while heating, (C'') the solvent, wherein the solvent (C'')
is at least one solvent selected from the group consisting of a
nitrogen-containing compound, a sulfur compound, a lactone, an
ether, a carbonate, a ketone, an alcohol, a phenol, an ester, a
hydrocarbon, and a halogenated hydrocarbon, and (D'') particles or
a liguid state material D each showing rubber elasticity.
24. A heat-resistant paste which comprises: (A'') a heat-resistant
resin A'' soluble in a solvent (C'') at room temperature and a
temperature at a time of drying while heating, (B'') a
heat-resistant resin B'' which is insoluble in the solvent (C'') at
room temperature but is soluble at a temperature at the time of
drying while heating, (C'') the solvent, wherein the solvent (C'')
is at least one solvent selected from the group consisting of
N-methylpyrrolidone, dimethylacetamide, dimethylformamide,
1,3-dimethyl-3,4,5,6-tetrahydro-2(1-H)-pyrimidinone,
1,3-dimethyl-2-imidazolidinone, sulforane, dimethylsulfoxide,
.gamma.-butyrolactone, .gamma.-valerolactone, .gamma.-caprolactone,
.gamma.-heptalactone, .alpha.-acetyl-.gamma.-butyrolactone,
.epsilon.-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene
glycol dimethyl (or diethyl, dipropyl, dibutyl) ether,
triethyleneglycol dimethyl ether, triethyleneglycol diethyl ether,
triethyleneglycol dipropyl ether, triethyleneglycol dibutyl ether,
tetraethyleneglycol dimethyl ether, tetraethyleneglycol diethyl
ether, tetraethyleneglycol dipropyl ether, tetraethyleneglycol
dibutyl ether, ethylene carbonate, propylene carbonate, methyl
ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone,
butanol, octyl alcohol, ethylene glycol, glycerin, diethylene
glycol monomethyl ether, diethylene glycol monoethyl ether,
triethylene glycol monomethyl ether, triethylene glycol monoethyl
ether, tetraethylene glycol monomethyl ether, tetraethylene glycol
monoethyl ether, phenol, cresol, xylenol, ethyl acetate, butyl
acetate, ethyl cellosolve acetate, butyl cellosolve acetate,
toluene, xylene, diethylbenzene, cyclohexane, trichioroethane,
tetrachloroethane, and monochlorobenzene, and (D'') particles or a
liquid state material D each showing rubber elasticity.
Description
TECHNICAL FIELD
This invention relates to a resin composition, a heat-resistant
resin paste and a semiconductor device using these and a method of
preparing the same, more specifically to a resin composition
excellent in adhesive property, heat-resistance and flexibility, a
heat-resistant paste which can provide a heat-resistant resin layer
which is widely utilized as a coating material, adhesive and stress
releasing material of a semiconductor device, is capable of
optionally controlling an elasticity and has a little temperature
dependency of the elasticity, and can provide such a heat-resistant
resin film, and a semiconductor device using these and a method of
preparing the same.
BACKGROUND ART
In recent years, electronic parts are becoming small sized and
thin, and it is an important technical task to relax a stress with
regard to a material applied to these parts. For example, with
regard to a material which is directly coating the electronic
parts, a high stress relaxing property is required. In particular,
whereas the size of the whole parts is becoming small, a chip
mounted thereon is becoming a large sized and thin so that a damage
caused by the stress at the time of curing or after curing is
likely caused. Under these background situations, the resin itself
is required to have less stress. In particular, for forming a
product in which a plural number of bear chips are mounted on the
same substrate like an IC card or a resin dam of a lead frame, a
slight residual stress at the time of curing becomes a cause of
breakage of wiring, warpage of a substrate or distortion of a
frame.
For forming a product on which a plural number of bear chips are
mounted on the same substrate like an IC chip or a resin dam of a
lead frame, an epoxy resin, etc., has conventionally been used, but
the resin has a large stress accompanied by shrinkage at curing so
that breakage of wiring or occurrence of crack after curing becomes
problems in a heat cycle test after curing or a solder reflow test.
Also, with regard to strain at the time of forming a resin dam on a
lead frame, a mold resin is flown out from the portion at which
strain occurs whereby there is a problem of molding failure at
molding.
To solve these problems, an attempt has been made in Japanese
Provisional Patent Publication No. 311520/1990 by adding a silicone
rubber elastic material to an epoxy resin composition whereby
providing a flexibility and relaxing stress. However, there are
problems that adhesiveness is lowered or resin strength is
lowered.
Also, in CSP (chip size package), a solder connecting portion is
plastically deformed in a semiconductor device in a surface
mounting type such as a bear chip packaging, by a stress caused by
the difference of thermal expansion coefficients between a
semiconductor element and a substrate, and when this is repeated,
the device is broken by fatigue. Thus, it has been carried out a
device to reduce a stress caused by the difference in the thermal
expansion coefficient of a substrate by providing an inter poser or
a stress relaxing layer between the semiconductor element and the
substrate. For example, in a semiconductor device shown in Japanese
Provisional Patent Publication No. 79362/1998, stress is relaxed by
making a bump high. Also, for the purpose of ensuring high
reliability of a package in a heat cycle test or a solder reflow
test, etc., a stress relaxing layer or an adhesive layer comprising
a low elasticity material to relax the difference of the thermal
expansion coefficients of a silicon chip and a substrate has been
used. Moreover, in a bear chip practical packaging, there is no
structure at the inside of the semiconductor to relax the stress so
that a device to reduce the stress caused by the difference of the
thermal expansion coefficients of the substrate has been carried
out by providing an underfill resin layer between the semiconductor
element and the substrate.
However, in the structure of relaxing a stress at the connecting
portion by the height of the bump as mentioned above, the stress is
rather concentrated to the bump itself so that there is a problem
of causing connection failure. Also, in the method of using the
underfill resin layer in combination, a resin is required to fill
in a narrow gap between the semiconductor device and the substrate
so that a filling operation is troublesome. Moreover, it is
difficult to fill the resin uniformly in the whole portion of the
gap so that there is a problem of lowering in production efficiency
of the semiconductor device.
In .mu.BGA (ball grid array) which is one example of CSP, a low
elastic material has been used for the purpose of ensuring
connection reliability between a lead from a "TAB" (tape automated
bonding) tape and an electrode on a silicon chip, and adhering the
TAB tape and the silicon chip.
Moreover, as a technique of integrating a wafer process and a
package process which had been completely separated, a wafer level
CSP process in which a package is prepared in a wafer state with
the same size as the chip size has been proposed. According to this
process, not only the production cost of the package can be reduced
but also wire length can be shortened so that there are merits that
a signal delay or noise in the package can be reduced and high
speed moving can be realized.
In this package, to ensure high reliability, it is necessary to use
a stress relaxing layer or an adhesive layer comprising a low
elastic material to relax the difference of the thermal expansion
coefficients between the silicon chip and the substrate as in the
conventional CSP such as .mu.BGA.
In the wafer level CSP process, to connect an electrode of the chip
to an outer practically mounting substrate, a metal layer which is
so-called a re-wiring layer is formed on a stress relaxing layer by
the sputtering method or the plating method, so that it is required
not only to be low elasticity but also to have resistances to
sputtering or plating.
However, the low elasticity material used in .mu.BGA is low
elasticity but is poor in heat resistance so that it has low
resistance to sputtering or plating whereby it cannot be applied to
the wafer level CSP process as such.
On the other hand, it has been carried out an attempt to relax the
stress by adding a monomer component having rubber elasticity to an
epoxy resin to lower the elasticity (Japanese Provisional Patent
Publication No. 48544/1986), but by using these components in
combination, there is a problem of lowering heat resistance of the
resin.
A thermoplastic resin having high heat resistance generally has
high resin elasticity and mechanical strength but is brittle so
that it is applied to electronic parts as such, there are high
possibility of causing inconveniences such as occurrences of
warpage of a substrate after curing or resin crack in a thermal
shock test. Thus, in Japanese Provisional Patent Publication No.
123824/1989, a method of copolymerizing a monomer component having
rubber elasticity in a resin has been proposed. However, this
method becomes a cause of lowering heat resistance of the resin
itself so that it is not preferred.
In recent years, a polyimide, polyamide imide or polyamide resin,
etc. excellent in heat resistance and mechanical resistance have
widely been used in the field of electronics for a surface
protective film or an interlayer insulating film of a semiconductor
element. Recently, as a producing method of these surface
protective film or interlayer insulating film, screen printing or
dispense coating has been attracted attention. Also, as a method of
forming a heat-resistant resin on a substrate such as chip, etc.,
spin coating method, screen printing method, dispense method, film
laminate method, etc., have been known.
A material which realizes screen printing, there may be mentioned a
material in which a filler is dispersed in a varnish such as a
heat-resistant polyimide resin, etc., as a binder to make a paste.
The filler of this material provide an effect of giving thixotropic
property to the paste. As the filler, there is a method of using
silica fine particles or heat-resistant insoluble polyimide fine
particles. However, these materials involve the problem that many
voids or bubbles are remained at the filler interface at heating
and drying so that film strength is weak. To solve these problems,
a heat-resistant resin paste as disclosed in Japanese Provisional
Patent Publication No. 289646/1990 has been developed. This is a
paste in which a filler of a polyamic acid is dispersed in a binder
of a polyamic acid, and at the time of heating and drying, the
filler is firstly dissolved and then, compatibilized with the
binder and forms a uniform coating film at the time of film
formation. However, it requires imidation step so that curing
conditions of 300.degree. C. or higher are required. Also, there
are problems that elasticity is high and flexibility is poor.
Moreover, in the other polyimide paste, similar problems are
involved.
In the spin coating method, there are problems in environmental
point and cost that a coating efficiency of the heat-resistant
resin solution is generally 10% or less (90% or more are lost
without coating to the substrate), etc. On the other hand, the
screen printing method using a metal plate or a mesh plate has
merits in the points that a heat-resistant resin can be coated only
the required parts within a short period of time effectively. Also,
the dispense method has merits that a heat-resistant resin can be
coated only the required parts without contacting the material to
be coated within a short period of time effectively.
As a heat-resistant resin paste which is capable of applying to
coating systems excellent in coating efficiency such as the screen
printing or the dispense, it has been reported in Japanese
Provisional Patent Publication No. 142252/1997 a heat-resistant
resin paste capable of forming a thick film pattern by using a
heat-resistant resin paste which dissolves in a solvent at the time
of heating and drying.
However, this heat-resistant resin has large elasticity so that
there is a problem that it cannot be used as such as a stress
relaxing material for relaxing the difference in thermal expansion
coefficients of a silicon chip and the substrate.
On the other hand, accompanying with the request of making an
electronic apparatus with a low cost, it has earnestly been desired
to obtain a semiconductor device which realizes the same
reliability with the conventional CSP and further the cost is
reduced. To cope with the low cost material, it has been proposed a
so-called wafer level CSP that is to obtain respective
semiconductor devices by forming semiconductor devices together on
a semiconductor wafer and then the wafer is cut. The reason why the
cost of the method can be reduced is that the packaging step can be
carried out on the wafer together so that a number of steps can be
reduced as compared with the conventional CSP in which each
semiconductor element cut from the wafer is treated, respectively.
More specifically, as disclosed in Japanese Provisional Patent
Publication No. 79362/1998, a Cu post is formed by an
electroplating on a semiconductor wafer, and after encapsulating
with a resin, the resin is polished until the top end portion of
the Cu post is exposed, and a solder ball is mounted on the exposed
Cu post top end portion and the semiconductor wafer is cut to the
respective semiconductor devices.
However, in the preparation method of a wafer level CSP
conventionally been proposed, a specific mold is required in many
cases in the method of using an encapsulating resin. Also, in the
method of using a spin coating step when an insulating layer is
formed on the wafer surface, there is much loss in a material to be
used, and there is a problem that a cost becomes much expensive
until a mass production technique is established.
An object of the present invention is to provide a resin
composition which can solve the above-mentioned problems, and gives
a film having high strength and low elasticity, and excellent in
flexibility only by a step of drying a solvent at 250.degree. C. or
lower, or by a step of drying a solvent at 250.degree. C. or lower
without imidation step.
Also, another object of the present invention is to provide a resin
composition capable of forming a precise pattern by screening
printing, dispense coating, etc. by giving thixotropic property of
the resin composition with an aromatic thermoplastic resin which is
insoluble in a polar solvent at room temperature but soluble by
heating.
Another object of the present invention is to provide a resin
composition capable of obtaining a coated film having the same
resin characteristics as the polyimide only by a step of drying a
solvent at 250.degree. C. or lower, or by a step of drying a
solvent at 250.degree. C. or lower without imidation step, and
giving a coated film having high strength and excellent
flexibility, and a semiconductor device using the same.
Further object of the present invention is to provide a
heat-resistant resin paste which is capable of widely utilizing for
a coating material, an adhesive, a stress relaxing material of a
semiconductor device, etc., of controlling elasticity optionally
and of forming a resin film excellent in heat resistance, has
thixotropic property and can be applied to coating systems
excellent in coating efficiency such as screen printing and
dispense coating, etc.
Still further object of the present invention is to provide a resin
for insulating a semiconductor device to be used for a resin layer
having high connection reliability by preventing line breakage at
the metal wiring or solder connecting portion caused by thermal
stress of a semiconductor device having a resin layer, and a
semiconductor device using the resin for the resin layer.
Still further object of the present invention is to provide a
method of producing a semiconductor device which controls loss of a
material at the minimum amount, prevents connection failure and
excellent in reliability, and a semiconductor device.
DISCLOSURE OF THE INVENTION
A resin composition of the present invention comprises (A) a
heat-resistant resin soluble in a solvent at room temperature, (B)
a heat-resistant resin which is insoluble in a solvent at room
temperature but becomes soluble by heating and (C) a solvent.
Also, the resin composition of the present invention also comprises
(A') an aromatic thermoplastic resin soluble in a polar solvent at
room temperature, (B') an aromatic thermoplastic resin which is
insoluble in a polar solvent at room temperature but is soluble by
heating and (C') an organic solvent.
Moreover, a heat-resistant resin paste of the present invention
comprises (A'') a heat-resistant resin A'' soluble in a solvent
(C'') at room temperature and a temperature at heating and drying,
(B'') a heat-resistant resin B'' which is insoluble in the solvent
(C'') at room temperature but is soluble at a temperature at the
time of heating and drying, (C'') the solvent, and (D) particles or
a liquid state material D showing rubber elasticity.
A semiconductor insulating resin of the present invention comprises
a resin which gives a resin layer having an elasticity at
25.degree. C. of 0.2 to 3.0 GPa, and an elasticity of said resin
layer at 150.degree. C. is 10 to 100% of that of at -65.degree. C.,
and said resin layer preferably has a glass transition temperature
of 180.degree. C. or higher.
A semiconductor device of the present invention comprises using the
above-mentioned resin composition, heat-resistant resin past or
semiconductor insulating resin.
A method of producing a semiconductor device according to the
present invention comprises a step of forming a plural number of
resin layers on a semiconductor substrate on which a first wiring
layer has been formed; a step of forming, on the resin layer, a
second wiring layer electrically connected to an electrode on the
semiconductor substrate; a step of forming a protective layer on
the second wiring layer except for a portion to which an outer
electrode terminal is mounted; and a step of forming the outer
electrode terminal on the second wiring layer.
A method of producing a semiconductor device according to the
present invention also comprises a step of forming a resin layer on
a semiconductor substrate on which a first wiring layer has been
formed; a step of providing a through hole(s) at part of the resin
layer penetrating to the first wiring layer; and a step of forming
a second wiring layer on the resin layer by which an outer
connection terminal and the first wiring layer are electrically
connected to each other.
A method of producing a semiconductor device according to the
present invention further comprises a step of forming a plural
number of resin layers on a semiconductor wafer on which a first
wiring layer has been formed by printing a resin having an
elasticity at 25.degree. C. of 0.2 to 3.0 GPa, a glass transition
temperature of 180.degree. C. or higher and a 5% weight-loss
temperature of 300.degree. C. or higher; a step of forming a second
wiring layer on the resin layer which is electrically connected to
an electrode on the semiconductor wafer; a step of forming a plural
number of protective layers of the second wiring layer by printing
the above resin on the second wiring layer; a step of providing a
through hole(s) at the protective layer of the second wiring layer
penetrating to of the second wiring layer; and a step of forming an
outer electrode terminal to the through hole(s); and a step of
cutting the semiconductor wafer to obtain respective semiconductor
devices.
BREIF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view showing preparation steps of a
semiconductor device to explain one example of the present
invention.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to a resin composition containing (A)
an aromatic thermoplastic resin soluble in a solvent at room
temperature, (B) an aromatic thermoplastic resin which is insoluble
in a solvent at room temperature but becomes soluble by heating and
(C) a solvent.
In the present invention, (A) the aromatic thermoplastic resin
soluble in a solvent at room temperature, and (B) the aromatic
thermoplastic resin which is insoluble in a solvent at room
temperature but becomes soluble by heating are preferably the
following resins: (A') A polyether amide imide or a polyether amide
soluble in a polar solvent at room temperature (B') A polyether
amide imide, a polyether amide or a polyether imide which is
insoluble in a polar solvent at room temperature but is soluble by
heating
In the present invention, the resin (A') is preferably obtained by
reacting the following constitutional components (1), (2) and (3),
or (1) and (3). (1) An aromatic diamine compound represented by the
following formula (I):
##STR00001## wherein R.sup.1, R.sup.2, R.sup.3 and R.sub.4 each
independently represent a hydrogen atom, an alkyl group having 1 to
9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms or a
halogen atom; X represents a single bonding arm, --O--, --S--,
--C(.dbd.O)--, --SO.sub.2--, --S(.dbd.O)-- or a group represented
by the following formula:
##STR00002## wherein R.sup.5 and R.sup.6 each independently
represent a hydrogen atom, an alkyl group, a trifluoromethyl group,
a trichloromethyl group, a halogen atom or a phenyl group, and each
of which may be the same or different from each other with the
recurring units, (2) a diamine compound comprising the following
constitutional components (a) and/or (b);
(a) an aromatic diamine compound other than the compound of the
formula (I),
(b) an aliphatic or alicyclic diamine compound, (3) an acid
compound comprising the following constitutional components (c)
and/or (d);
(c) a dicarboxylic acid or a reactive acid derivative thereof,
(d) a tricarboxylic acid or a reactive acid derivative thereof.
In the present invention, when the resin (B') is a polyether amide
imide or a polyether amide, a resin obtained by reacting the
following constitutional components (1), (2) and (3), or (1) and
(3) is preferred. (1) An aromatic diamine compound represented by
the above-mentioned formula (I); (2) a diamine compound comprising
the following constitutional components (a) and/or (b);
(a) an aromatic diamine compound other than the compound of the
formula (I),
(b) an aliphatic or alicyclic diamine compound, (3) an acid
compound comprising the following constitutional components (c)
and/or (d) and a tetracarboxylic acid dianhydride represented by
the following formula (II) or a reactive acid derivative
thereof;
(c) a dicarboxylic acid or a reactive acid derivative thereof,
(d) a tricarboxylic acid or a reactive acid derivative thereof,
##STR00003## wherein Y represents a single bonding arm, --O--,
--S--, --C(.dbd.O)--, --SO.sub.2--, --S(.dbd.O)--, a group
represented by the following formula, or a divalent aromatic
hydrocarbon group, aliphatic hydrocarbon group or alicyclic
hydrocarbon group, and each of which may be the same or different
from each other with the recurring units,
##STR00004## wherein R.sub.5 and R.sub.6 have the same meanings as
defined above.
In the present invention, when the resin (B') is a polyether imide,
a resin obtained by reacting the following constitutional
components (1), (2) and (3), or (1) and (3) is preferred. (1) An
aromatic diamine compound represented by the above-mentioned
formula (I); (2) a diamine compound comprising the following
constitutional components (a) and/or (b);
(a) an aromatic diamine compound other than the compound of the
formula (I),
(b) an aliphatic or alicyclic diamine compound, (3) a
tetracarboxylic acid dianhydride represented by the above-mentioned
formula (II) or a reactive acid derivative thereof.
In the present specification, room temperature means a temperature
condition in which a treatment is carried out without conducting
any specific designation or control, or the case where a sample or
a substance is allowed to stand in a room, and is not specifically
limited, and it is preferably a temperature in the range of 10 to
40.degree. C.
Also, heating means an action of elevating the temperature of a
sample or a substance at the room temperature or higher, and is not
specifically limited by the temperature, and it is preferably
elevating the temperature to 50.degree. C. or higher.
The polyether amide imide or the polyether amide in the present
invention is preferably a resin containing the following ether
group: --O-- and an amide group or an imide group of the following
formulae (i), (ii) or (iii) as a recurring unit.
##STR00005## wherein Z.sup.1 represents a trivalent aromatic
hydrocarbon group, aliphatic hydrocarbon group or alicyclic
hydrocarbon group,
##STR00006## wherein Z.sup.2 represents a divalent aromatic
hydrocarbon group, aliphatic hydrocarbon group or alicyclic
hydrocarbon group,
##STR00007## wherein Z.sup.3 represents a tetravalent aromatic
hydrocarbon group, aliphatic hydrocarbon group or alicyclic
hydrocarbon group.
Also, the polyether imide in the present invention is preferably a
resin having the ether group of the above-mentioned formula and the
imide group represented by the formula (iii) as a recurring
unit.
The polar solvent in the present invention is not specifically
limited so long as it is a solvent constituted by a molecule having
a polarity, and, for example, it may include a protonic solvent in
which it is easily dissociated and releases a proton (H.sup.+) such
as an alcohol, a carboxylic acid, etc., or an aprotic solvent in
which no proton (H.sup.+) is released by dissociation, and the
like. There may be preferably mentioned an aprotic solvent such as
acetonitrile, dimethoxyethane, dimethylformamide (DMF),
dimethylsulfoxide (DMSO), hexamethyl phosphoric acid triamide
(HMPA), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc),
.gamma.-butyrolactone, etc.; an ether such as diethylene glycol
dimethyl ether, diethylene glycol diethyl ether, diethylene glycol
dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol
dimethyl ether, triethylene glycol diethyl ether, triethylene
glycol dipropyl ether, triethylene glycol dibutyl ether,
tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl
ether, tetraethylene glycol dipropyl ether, tetraethylene glycol
dibutyl ether, diethylene glycol monomethyl ether, diethylene
glycol monoethyl ether, diethylene glycol dimethyl ether,
triethylene glycol dimethyl ether, triethylene glycol monomethyl
ether, triethylene glycol monoethyl ether, tetraethylene glycol
monomethyl ether, tetraethylene glycol monoethyl ether, etc.
As the aromatic diamine compound having an ether bond represented
by the above-mentioned formula (I) in the present invention, there
may be mentioned, for example,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]butane,
2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]butane,
2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]butane,
2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]butane,
1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane,
1,1,1,3,3,3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane,
1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane,
1,1-bis[4-(4-aminophenoxy)phenyl]cyclopentane,
bis[4-(4-aminophenoxy)phenyl]sulfone,
bis[4-(4-aminophenoxy)phenyl]ether,
4,4'-carbonylbis(p-phenyleneoxy)dianiline,
4,4'-bis(4-aminophenoxy)biphenyl, etc., and of these, 2,2-bis
[4-(4-aminophenoxy)phenyl]propane is preferred. If necessary, the
above-mentioned aromatic diamine compound may be used in
combination of two or more kinds.
In the present invention, a formulation amount of the aromatic
diamine compound represented by the formula (I) is preferably 0.1
to 99.9 mol %, more preferably 15 to 99.9 mol %, further preferably
30 to 99.9 mol % based on the total amount of the diamine
component.
As the aromatic diamine compound other than those represented by
the formula (I) in the present invention, there may be mentioned,
for example, m-phenylenediamine, p-phenylenediamine,
diamino-m-xylylene, diamino-p-xylylene, 1,4-dinaphthalenediamine,
2,6-dinaphthalenediamine, 2,7-dinaphthalenediamine,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
3,4'-diaminobiphenyl, 4,4'-diaminobenzophenone,
3,3'-diaminobenzophenone, o-toluidine, 2,4-toluylenediamine,
1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene,
1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene,
bis[4-(3-aminophenoxy)phenyl]sulfone,
4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenylsulfide,
3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide,
2,2-bis(4-aminophenyl)propane,
2,2-bis(4-aminophenyl)hexafluoropropane,
2,2-bis(3-amino-4-methylphenyl)propane,
2,2-bis(3-amino-4-methylphenyl)hexafluoropropane,
2,2'-dimethyl-benzidine, 2,2'-bis(trifluoromethyl)benzidine,
4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane,
4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane,
4,4'-diamino-3,3',5,5'-tetra-n-propyldiphenylmethane,
4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane,
4,4'-diamino-3,3',5,5'-tetrabutyldiphenylmethane,
4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane,
4,4'-diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane,
4,4'-diamino-3,3'-diethyl-5,5'-diisopropyldiphenylmethane,
4,4'-diamino-3,5-dimethyl-3',5'-diethyldiphenylmethane,
4,4'-diamino-3,5-dimethyl-3',5'-diisopropyldiphenylmethane,
4,4'-diamino-3,5-diethyl-3',5'-diisopropyldiphenylmethane,
4,4'-diamino-3,5-diethyl-3',5'-dibutyldiphenylmethane,
4,4'-diamino-3,5-diisopropyl-3',5'-dibutyldiphenylmethane,
4,4'-diamino-3,3'-diisopropyl-5,5'-dibutyldiphenylmethane,
4,4'-diamino-3,3'-dimethyl-5,5'-dibutyldiphenylmethane,
4,4'-diamino-3,3'-diethyl-5,5'-dibutyldiphenylmethane,
4,4'-diamino-3,3'-dimethyldiphenylmethane,
4,4'-diamino-3,3'-diethyldiphenylmethane,
4,4'-diamino-3,3'-di-n-propyldiphenylmethane,
4,4'-diamino-3,3'-diisopropyldiphenylmethane,
4,4'-diamino-3,3'-dibutyldiphenylmethane,
4,4'-diamino-3,3',5-trimethyldiphenylmethane,
4,4'-diamino-3,3',5-triethyldiphenylmethane,
4,4'-diamino-3,3',5-tri-n-propyldiphenylmethane,
4,4'-diamino-3,3',5-triisopropyldiphenylmethane,
4,4'-diamino-3,3',5-tributyldiphenylmethane,
4,4'-diamino-3-methyl-3'-ethyldiphenylmethane,
4,4'-diamino-3-methyl-3'-isopropyldiphenylmethane,
4,4'-diamino-3-ethyl-3'-isopropyldiphenylmethane,
4,4'-diamino-3-ethyl-3'-isobutyldiphenylmethane,
4,4'-diamino-3-isopropyl-3'-butyldiphenylmethane,
4,4'-diamino-2,2'-bis(3,3',5,5'-tetramethyldiphenyl)isopropane,
4,4'-diamino-2,2'-bis(3,3',5,5'-tetraethyldiphenyl)isopropane,
4,4'-diamino-2,2'-bis(3,3', 5,5'-tetra-n-propyldiphenyl)isopropane,
4,4'-diamino-2,2'-bis(3,3',5,5'-tetraisopropyldiphenyl)isopropane,
4,4'-diamino-2,2'-bis(3,3',5,5'-tetrabutyldiphenyl)isopropane,
4,4'-diamino-3,3',5,5'-tetramethyldiphenyl ether,
4,4'-diamino-3,3',5,5'-tetraethyldiphenyl ether,
4,4'-diamino-3,3',5,5'-tetra-n-propyldiphenyl ether,
4,4'-diamino-3,3', 5,5'-tetraisopropyldiphenyl ether,
4,4'-diamino-3,3',5,5'-tetrabutyldiphenyl ether,
4,4'-diamino-3,3',5,5'-tetramethyldiphenyl sulfone,
4,4'-diamino-3,3',5,5'-tetraethyldiphenyl sulfone,
4,4'-diamino-3,3',5,5'-tetra-n-propyldiphenyl sulfone,
4,4'-diamino-3,3',5,5'-tetraisopropyldiphenyl sulfone,
4,4'-diamino-3,3',5,5'-tetrabutyldiphenyl sulfone,
4,4'-diamino-3,3',5,5'-tetramethyldiphenyl ketone,
4,4'-diamino-3,3',5,5'-tetraethyldiphenyl ketone,
4,4'-diamino-3,3',5,5'-tetra-n-propyldiphenyl ketone,
4,4'-diamino-3,3',5,5'-tetraisopropyldiphenyl ketone,
4,4'-diamino-3,3',5,5'-tetrabutyldiphenyl ketone,
4,4'-diamino-3,3',5,5'-tetramethyl benzanilide,
4,4'-diamino-3,3',5,5'-tetraethyl benzanilide,
4,4'-diamino-3,3',5,5'-tetra-n-propyl benzanilide,
4,4'-diamino-3,3',5,5'-tetraisopropyl benzanilide,
4,4'-diamino-3,3',5,5'-tetrabutyl benzanilide,
metatoluilenediamine, 4,4'-diaminodiphenylethane,
1,4-bis(4-aminocumyl)benzene (BAP), 1,3-bis(4-aminocumyl)benzene,
1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene,
1,4-bis(4-aminophenoxy)benzene,
2,2-bis[4-(3-aminophenoxy)phenyl]propane,
bis[4-(3-aminophenoxy)phenyl]sulfone (m-APPS),
bis[4-(4-aminophenoxy)phenyl]sulfone,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, etc. If
necessary, the above-mentioned aromatic diamine compound may be
used in combination of two or more kinds.
In the present invention, a formulation amount of the aromatic
diamine compound other than the aromatic diamine compound
represented by the formula (I) is preferably 0.1 to 99.9 mol %,
more preferably 15 to 99.9 mol %, further preferably 30 to 99.9 mol
% based on the total amount of the diamine component.
As the aliphatic or alicyclic diamine compound in the present
invention, it is not specifically limited so long as it is a
compound in which an amino group is bonded to an aliphatic or
alicyclic hydrocarbon, and there may be mentioned, for example, an
aliphatic diamine compound such as 1,2-diaminoethane,
1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane,
1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane,
1,12-diaminododecane,
3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (ATU),
methylpentamethylenediamine (MPMD), trimethylhexamethylene diamine
(TMD), etc., an alicyclic diamine compound such as
1,2-diaminocyclohexane, methylenediaminocyclohexamine (PACM),
norbornanediamine (NBDA), etc., diaminosiloxane, a diamine compound
in which the main chain is a copolymer of ethylene oxide, propylene
oxide, or ethylene oxide and propylene oxide, a diamine compound in
which the main chain is rubber, etc. If necessary, the
above-mentioned aliphatic or alicyclic diamine compound may be used
in combination of two or more kinds.
In the present invention, a formulation amount of the aliphatic or
alicyclic diamine compound is preferably 0.1 to 95 mol %, more
preferably 0.1 to 90 mol %, further preferably 0.1 to 85 mol %
based on the total amount of the diamine component.
In the present invention, the aliphatic or alicyclic diamine
compound (b) preferably contains diaminosiloxane represented by the
following formula (III):
##STR00008## wherein R.sup.7 and R.sup.8 each represent a divalent
hydrocarbon group, R.sup.9 to R.sup.12 each represent an alkyl
group having 1 to 9 carbon atoms, a phenyl group or a phenyl group
substituted by an alkyl group and n is an integer of 1 to 30.
As the diaminosiloxane represented by the above-mentioned formula
(III), there may be mentioned, for example, X-22-161AS, X-22-161A,
X-22-161B (all trade names, available from Shin-etsu Kagaku Kogyo
K.K., Japan), BY16-853U, BY16-853, BY16-853B (all trade names,
available from Dow Corning Toray Silicone Co., Ltd., Japan),
TSL9386, TSL9346, TSL9306 (all trade names, available from Toshiba
Silicone, K.K., Japan), F2-053-01 (trade name, available from
Nippon Unicar, Japan), etc. If necessary, the above-mentioned
diaminosiloxane may be used in combination of two or more
kinds.
In the present invention, a formulation amount of the
diaminosiloxane is preferably 0.1 to 99.9 mol %, more preferably
0.1 to 95 mol %, further preferably 0.1 to 90 mol % based on the
total amount of the diamine component.
As the above-mentioned dicarboxylic acid or a reactive acid
derivative thereof in the present invention, there may be
mentioned, for example, an aliphatic dicarboxylic acid such as
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic
acid, pimellic acid, suberic acid, azelaic acid, sebacic acid,
undecanoic diacid, dodecanoic diacid, tridecanoic diacid,
cyclohexane dicarboxylic acid, dimeric acid, etc., an aromatic
dicarboxylic acid such as phthalic acid, isophthalic acid,
terephthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid,
4,4'-diphenylether dicarboxylic acid, 4,4'-diphenylsulfone
dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, etc., and a
reactive acid derivative thereof, and terephthalic acid and
isophthalic acid, and their reactive acid derivatives are preferred
since they are easily available. If necessary, the above-mentioned
dicarboxylic acid or a reactive acid derivative thereof may be used
in combination of two or more kinds.
In the present invention, a formulation amount of the dicarboxylic
acid or a reactive acid derivative thereof is preferably 80 to 150
mol %, more preferably 90 to 150 mol % based on the total amount of
the diamine component.
As the above-mentioned tricarboxylic acid or a reactive acid
derivative thereof, there may be mentioned trimellitic acid,
3,3,4'-benzophenone tricarboxylic acid, 2,3,4'-diphenyl
tricarboxylic acid, 2,3,6-pyridine tricarboxylic acid,
3,4,4'-benzanilide tricarboxylic acid, 1,4,5-naphthalene
tricarboxylic acid, 2'-methoxy-3,4,4'-diphenylether tricarboxylic
acid, 2'-chlorobenzanilide-3,4,4'-tricarboxylic acid, etc. Also, as
a reactive acid derivative of the above-mentioned tricarboxylic
acid, there may be mentioned an acid anhydride, halide, ester,
amide, ammonium salt of the above-mentioned aromatic tricarboxylic
acid, and their examples may include trimellitic anhydride,
trimellitic anhydride monochloride,
1,4-dicarboxy-3-N,N-dimethylcarbamoylbenzene,
1,4-dicarbomethoxy-3-carboxybenzene,
1,4-dicarboxy-3-carbophenoxybenzene,
2,6-dicarboxy-3-carbomethoxypyridine,
1,6-carboxy-5-carbamoylnaphthalene, an ammonium salt comprising the
above-mentioned aromatic tricarboxylic acid and ammonia,
dimethylamine, triethylamine, etc. Of these, trimellitic anhydride
and trimellitic anhydride monochloride are preferred.
If necessary, the above-mentioned tricarboxylic acid or a reactive
acid derivative thereof may be used in combination of two or more
kinds.
In the present invention, a formulation amount of the tricarboxylic
acid or a reactive acid derivative thereof is preferably 80 to 150
mol %, more preferably 90 to 150 mol % based on the total amount of
the diamine component.
As the tetracarboxylic acid dianhydride represented by the
above-mentioned formula (II) or a reactive acid derivative thereof,
there maybe mentioned, for example, a tetracarboxylic acid
dianhydride such as 3,3',4,4'-biphenyltetracarboxylic acid
dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride,
2,3,3',4'-biphenyltetracarboxylic acid dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)sulfone dianhydride,
bis(3,4-dicarboxyphenyl)ether dianhydride,
3,4,3',4'-benzophenonetetracarboxylic acid dianhydride,
2,3,2',3'-benzophenonetetracarboxylic acid dianhydride,
2,3,3',4'-benzophenonetetracarboxylic acid dianhydride,
bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride,
bis(3,4-dicarboxyphenyl)methylphenylsilane dianhydride,
bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride,
1,4-bis(3,4-dicarboxyphenyldimethylsilyl)benzene dianhydride,
1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane
dianhydride,
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane
dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane
dianhydride, 4,4-bis(3,4-dicarboxyphenoxy)diphenylsulfide
dianhydride, etc., and their reactive acid derivatives, etc. Here,
3,4,3',4'-benzophenonetetracarboxylic acid dianhydride or
bis(3,4-dicarboxyphenyl)ether dianhydride is preferred. If
necessary, the above-mentioned tetracarboxylic acid or a reactive
acid derivative thereof may be used in combination of two or more
kinds.
In the resin composition of the present invention, (C') an organic
acid is not particularly limited, and may be mentioned, for
example, a nitrogen-containing compound such as
N-methylpyrrolidone, dimethylacetamide, dimethylformamide, etc.; a
sulfur-containing compound such as sulforane, dimethylsulfoxide,
etc.; a lactone such as .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .gamma.-heptalactone,
.alpha.-acetyl-.gamma.-butyrolactone, .epsilon.-caprolactone, etc.;
a ketone such as methyl ethyl ketone, methyl isobutyl ketone,
cyclohexanone, acetophenone, etc.; an ether such as ethylene
glycol, glycerin, diethylene glycol dimethyl ether, diethylene
glycol diethyl ether, diethylene glycol dipropyl ether, diethylene
glycol dibutyl ether, triethylene glycol dimethyl ether,
triethylene glycol diethyl ether, triethylene glycol dipropyl
ether, triethylene glycol dibutyl ether, tetraethylene glycol
dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene
glycol dipropyl ether, tetraethylene glycol dibutyl ether,
diethylene glycol monomethyl ether, diethylene glycol monoethyl
ether, triethylene glycol monomethyl ether, triethylene glycol
monoethyl ether, tetraethylene glycol monomethyl ether,
tetraethylene glycol monoethyl ether, etc.
A formulation amount of (C') the organic solvent is preferably 100
to 3500 parts by weight, more preferably 150 to 1000 parts by
weight based on 100 parts by weight of the total resin amount.
In the present invention, when a polyether amide imide or a
polyether amide is to be obtained, the tetracarboxylic acid or a
reactive acid derivative thereof is preferably used in an amount of
0.1 to 90 mol %, more preferably 0.1 to 80 mol % based on the total
amount of the diamine component.
In the present invention, when a polyether imide is to be obtained,
the tetracarboxylic acid or a reactive acid derivative thereof is
preferably used in an amount of 80 to 200 mol %, more preferably 90
to 180 mol % based on the total amount of the diamine
component.
In the present invention, an acid compound which is the
above-mentioned dicarboxylic acid or a reactive acid derivative
thereof and the tricarboxylic acid or a reactive acid derivative
thereof alone or in combination thereof is preferably used in an
amount of 80 to 140 mol %, more preferably 90 to 120 mol % based on
the total amount of the diamine component. When they are used in
equimolar amount to the total amount of the diamine compound, a
compound having the highest molecular weight tends to be
obtained.
In the present invention, an acid compound which is the
above-mentioned dicarboxylic acid or a reactive acid derivative
thereof and the tricarboxylic acid or a reactive acid derivative
thereof alone or in combination thereof and a combination thereof
with the tetracarboxylic acid dianhydride represented by the
formula (II) or a reactive acid derivative thereof is preferably
used in an amount of 80 to 140 mol %, more preferably 90 to 120 mol
% based on the total amount of the diamine component. When they are
used in equimolar amount to the total amount of the diamine
compound, a compound having the highest molecular weight tends to
be obtained.
For synthesizing the above-mentioned compounds of the present
invention, a conventionally known method which has been used in the
reaction of the diamine component and the acid component can be
employed as such, and various conditions are not particularly
limited and the conventionally known method can be used. This
reaction is carried out in an organic solvent. As such an organic
solvent, there may be mentioned, for example, a nitrogen-containing
compound such as N-methylpyrrolidone, dimethylacetamide,
dimethylformamide,
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone,
1,3-dimethyl-2-imidazolidinone, etc.; a sulfur-containing compound
such as sulforane, dimethylsulfoxide, etc.; a lactone such as
.gamma.-butyrolactone, .gamma.-valerolactone, .gamma.-caprolactone,
.gamma.-heptalactone, .alpha.-acetyl-.gamma.-butyrolactone,
.epsilon.-caprolactone, etc.; a ketone such as methyl ethyl ketone,
methyl isobutyl ketone, cyclohexanone, acetophenone, etc.; an ether
such as ethylene glycol, glycerin, diethylene glycol dimethyl
ether, diethylene glycol diethyl ether, diethylene glycol dipropyl
ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl
ether, triethylene glycol diethyl ether, triethylene glycol
dipropyl ether, triethylene glycol dibutyl ether, tetraethylene
glycol dimethyl ether, tetraethylene glycol diethyl ether,
tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl
ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, triethylene glycol monomethyl ether, triethylene
glycol monoethyl ether, tetraethylene glycol monomethyl ether,
tetraethylene glycol monoethyl ether, etc.; a phenol such as
phenol, cresol, xylenol, etc.; an ester such as ethyl acetate,
butyl acetate, ethyl cellosolve acetate ("cellosolve" is trade
name), butyl cellosolve acetate ("cellosolve" is trade name), etc.;
a hydrocarbon such as toluene, xylene, diethylbenzene, cyclohexane,
etc.; a halogenated hydrocarbon such as trichloroethane,
tetrachloroethane, methylene chloride, chloroform,
monochlorobenzene, etc. These may be used alone or in combination
of two or more.
These reactions may be carried out in the above-mentioned organic
solvents by reacting the diamine compound and the acid compound
preferably at -78 to 100.degree. C., more preferably-50 to
60.degree. C. In the reaction, an inorganic acid acceptor may be
added in an amount of 90 to 400 mol % based on the total amount of
the diamine compound. Such an inorganic acid acceptor may be
mentioned, for example, a tertiary amine such as triethylamine,
tripropylamine, tributylamine, triamylamine, pyridine, etc.; a
1,2-epoxide such as propylene oxide, styrene oxide, cyclohexene
oxide, etc. Accompanying with the progress of the reaction, a
viscosity of the reaction mixture becomes gradually high. In this
case, a polyamic acid which is a precursor of the polyether amide
imide is formed. This polyamic acid is subjected to imidation by
dehydration ring-closure reaction to give a polyether amide imide.
In this dehydration ring-closure reaction, there are a thermal
ring-closure method in which the dehydration reaction is carried
out by heating to 80 to 400.degree. C., a chemical ring-closure
method by using a dehydrating agent, and the like.
In the case of the heat ring-closure method, it is preferably
carried out while removing water generating in the dehydration
reaction outside the reaction system. At this time, the reaction is
carried out by heating a reaction solution preferably to 80 to
400.degree. C., more preferably 100 to 250.degree. C. During the
reaction, water may be removed by azeotropic distillation by using
a solvent which evaporates with water such as benzene, toluene,
xylene, etc.
In the case of the chemical ring-closure method, the reaction is
carried out in the presence of a chemical dehydrating agent
preferably at 0 to 120.degree. C., more preferably 10 to 80.degree.
C. As the chemical dehydrating agent, there may be used, for
example, an acid anhydride such as acetic anhydride, propionic
anhydride, butyric anhydride, benzoic anhydride, etc., a
carbodiimide compound such as dicyclohexylcarbodiimide, etc. At
this time, the reaction is preferably carried out by using a
substance which promotes the cyclization reaction such as pyridine,
isoquinoline, trimethylamine, triethylamine, aminopyridine,
imidazole, etc. in combination. The chemical dehydrating agent is
preferably used in an amount of 90 to 600 mol % based on the total
amount of the diamine compound, and the substance which promotes
the cyclization reaction is preferably used in an amount of 40 to
300 mol % based on the same. Also, a dehydrating catalyst including
a phosphorus compound such as triphenylphosphite,
tricyclohexylphosphite, triphenylphosphate, phosphoric acid,
phosphor pentoxide, etc., a boron compound such as boric acid,
anhydrous boric acid, etc., may be used.
The reaction mixture completed in imidation by the dehydration
reaction is poured into a far excessive amount of a solvent which
is compatible with the above-mentioned organic solvent and is a
poor solvent to the resulting resin such as a lower alcohol
including methanol, etc., and resulting precipitates of the resin
is obtained by filtration and the solvent is removed by drying to
obtain the polyether amide imide of the present invention. The
polyether imide of the present invention can be obtained according
to the same synthetic method as in the polyether amide imide.
In the polyether amide imide or polyether amide which is soluble in
a polar solvent at the room temperature, and the polyether amide
imide, polyether amide or polyether imide which is insoluble in a
polar solvent at the room temperature but soluble by heating
obtained by the above-mentioned method, their formulation amount is
not specifically limited, and an optional formulation amount can be
employed. It is preferred that the amount of the polyether amide
imide, polyether amide or polyether imide which is insoluble in a
polar solvent at the room temperature but soluble by heating is 10
to 300 parts by weight, more preferably 10 to 200 parts by weight
based on 100 parts by weight of the polyether amide imide or
polyether amide which is soluble in a polar solvent at the room
temperature.
A method of preparing the resin composition according to the
present invention, i.e., the resin composition comprising two kinds
of resins of the polyether amide imide or polyether amide which is
soluble in a polar solvent at the room temperature, and the
polyether amide imide, polyether amide or polyether imide which is
insoluble in a polar solvent at the room temperature but soluble by
heating, and an organic solvent, is not particularly limited. For
example, the polyether amide imide or polyether amide which is
soluble in a polar solvent at the room temperature is dissolved in
an organic solvent to obtain a varnish, then, the polyether amide
imide, polyether amide or polyether imide which is insoluble in a
polar solvent at the room temperature but soluble by heating is
added to the varnish, and the mixture is heated to 50 to
200.degree. C. to uniformly dissolve the resins and allowed to
stand for cooling the mixture to obtain a past of the resin
composition containing two kinds of the resins.
In the resin composition of the present invention, a low elasticity
filler and/or liquid state rubber each having rubber elasticity is
preferably contained.
As the low elasticity filler and/or liquid state rubber each having
rubber elasticity, it is not specifically limited, and a filler of
an elastic material such as acrylic rubber, fluorine rubber,
silicone rubber, butadiene rubber, etc.; or liquid state rubber
thereof may be mentioned. Here, in view of heat resistance of the
resin composition, silicone rubber is preferably used. Also, it is
preferred to use a filler on the surface of which has been
subjected to chemical modification by an epoxy group. In place of
the epoxy group as mentioned above, those modified by a functional
group such as an amino group, an acrylic group, a vinyl group, a
phenyl group, etc. By adding these low elasticity filler to the
resin composition or a thermoplastic resin having heat resistance,
it is possible to make the resulting material low elasticity and to
control a modulus of elasticity without impairing heat resistance
and adhesiveness.
An average particle size of the low elasticity filler having rubber
elasticity the surface of which has been chemically modified to be
used in the resin composition of the present invention is
preferably 0.1 to 50 .mu.m and finely pulverized in sphere shape or
amorphous shape. If the average particle size is less than 0.1
.mu.m, aggregation between the particles likely occurs and it tends
to be difficult to sufficiently disperse the particles. Also, if it
exceeds 50 .mu.m the surface of the coated film becomes rough and a
uniformly coated film tends to be hardly obtained.
In the resin composition of the present invention, a formulation
amount of the low elasticity filler having rubber elasticity the
surface of which is chemically modified is preferably 5 to 900
parts by weight, more preferably 5 to 800 parts by weight based on
100 parts by weight of the total amount of the aromatic
thermoplastic resin.
In the present invention, by using silicone rubber as the low
elasticity filler having rubber elasticity the surface of which is
chemically modified and varying a formulation amount thereof, the
modulus of elasticity of the resulting material can be controlled
in the range of 0.2 to 3.0 GPa, and the modulus of elasticity at
150.degree. C. can be controlled to a value within 10 to 100% of
that at -65.degree. C. This characteristic is effective at the time
of measuring a temperature cycle test from -55.degree. C. to
150.degree. C. as a reliability evaluation when a semiconductor
device is prepared. Also, the resin composition become a low
elasticity material while maintaining heat resistance that the
glass transition temperature is 180.degree. C. or higher and the
thermal decomposition temperature is 300.degree. C. or higher.
The resin composition according to the present invention, i.e., the
resin composition comprising two kinds of resins of the polyether
amide imide or polyether amide which is soluble in a polar solvent
at the room temperature, the polyether amide imide, polyether amide
or polyether imide which is insoluble in a polar solvent at the
room temperature but soluble by heating, the low elasticity filler
and the organic solvent can be obtained by adding the low
elasticity filler to the varnish of the aromatic thermoplastic
resin, and kneading and stirring by a dispersing machine such as a
stirrer, a triple roll mill, a ball mill, a planetary mixer, a
disper, a homogenizer, etc. to obtain a resin composition.
In the resin composition of the present invention, an additive or a
resin modifier such as a colorant, a coupling agent, etc. may be
further added. As the colorant, there may be mentioned carbon
black, dye, pigment, etc., and as the coupling agent, an aluminate
type coupling agent, a silane type coupling agent, a titanate type
coupling agent, a thiol type coupling agent, etc.
The above-mentioned additives may be preferably added in an amount
of 50 parts by weight or less based on 100 parts by weight of the
total amount of the aromatic thermoplastic resin.
Next, the heat-resistant resin paste of the present invention is
explained below.
The heat-resistant resin paste of the present invention may be
obtained by making the above-mentioned resin composition as a paste
or the following is also preferred.
That is, the heat-resistant resin paste of the present invention
comprises (A'') a heat-resistant resin A'' which is soluble in a
solvent (C'') at room temperature and a temperature at the time of
heating and drying, (B'') a heat-resistant resin B'' which does not
dissolve in a solvent (C'') at room temperature but dissolve at a
temperature at the time of heating and drying, (C'') a solvent C
and (D) particles or a liquid material D showing rubber
elasticity.
Also, the heat-resistant resin paste of the present invention
preferably comprises that (A'') the heat-resistant resin A'' and
(B'') the heat-resistant resin B'' are each an aromatic polyimide
type resin obtained by reacting an aromatic tetracarboxylic acid
dianhydride and an aromatic diamine, and the main component of (D)
the particles showing rubber elasticity is silicone rubber.
Moreover, in the heat-resistant resin paste of the present
invention, it is preferred that (B'') heat-resistant resin B'' is
an aromatic polyimide type resin obtained by reacting an aromatic
tetracarboxylic acid dianhydride containing 50 mol % or more of
3,4,3',4'-benzophenone tetracarboxylic acid dianhydride and an
aromatic diamine containing 50 mol % or more of
4,4'-diaminodiphenyl ether, and the main solvent of (C'') is
.gamma.-butyrolactone.
As (A'') the heat-resistant resin A'' which is soluble in a solvent
(C'') at room temperature and a temperature at the time of heating
and drying, it is preferred to use a material which forms a uniform
phase with the heat-resistant resin B'' of (B'') after heating and
drying when the heat-resistant resin paste film is formed by a
screen printing, etc., and a film pattern is formed by heating and
drying.
That is, it is preferred to use a material which dissolves well in
a solvent at a temperature at the time of heating and drying, and
well compatible with the heat-resistant resin B'' of (B'') after
heating and drying.
More specifically, for example, a heat-resistant resin having an
amide group, an imide group, an ester group or an ether group is
preferably used. Moreover, there may be specifically mentioned a
polyimide resin, a polyamide imide resin, a polyamide resin, a
polyester resin, a polyether resin, etc. With regard to the
polyimide resin and the polyamide imide resin, a resin comprising a
polyamic acid which is a precursor thereof or a partially imidated
polyamic acid may be used.
When the heat-resistance is considered, it is preferred that a 5%
thermal weight loss temperature of (A'') the heat-resistant resin
A'' is 300.degree. C. or higher. If it is lower than 300.degree.
C., at the heat treatment step at a high temperature, e.g., at the
time of mounting a solder ball, an out gas is likely generated and
there is a tendency that reliability of a semiconductor device can
be difficultly obtained.
When easiness of synthesis, heat-resistance and preservation
stability of the paste are considered, it is preferred to use a
polyimide resin, and an aromatic polyimide type resin (for example,
a polyamic acid obtained by reacting an aromatic tetracarboxylic
acid dianhydride and an aromatic diamine, a polyimide in which the
above polyamic acid is imidated, etc.) is particularly
preferred.
(B'') the heat-resistant resin B'' which does not dissolve in a
solvent (C'') at room temperature but dissolve at a temperature at
the time of heating and drying is used for giving thixotropic
property to the paste.
As the heat-resistant resin A'' of (A''), that which is soluble in
a solvent at room temperature is used, while as (B'') the
heat-resistant resin B'', that which is not soluble in the solvent
of (C'') at room temperature is used, but both of the resins have
properties soluble in the respective solvents at the temperature at
the time of heating and drying.
Also, in the viewpoint of uniformity and mechanical characteristics
of the film obtained by heating and drying the heat-resistant resin
paste of the present invention, (A'') the heat-resistant resin A''
and (B'') the heat-resistant resin B'' preferably have
compatibility after heating and drying, and in particular, it is
preferred that (A'') the heat-resistant resin A'' and (B'') the
heat-resistant resin B'' form a uniform phase after heating and
drying. This uniform phase may contain an organic solvent remained
after heating and drying.
As (B'') the heat-resistant resin B'', a heat-resistant resin
having an amide group, an imide group, an ester group or an ether
group is preferably used. As said heat-resistant resin, in the
viewpoint of heat-resistance and mechanical characteristics, a
polyimide resin or a precursor thereof, a polyamide imide resin or
a precursor thereof or a polyamide resin is preferably used.
As the polyimide resin or the precursor thereof, the polyamide
imide resin or the precursor thereof or the polyamide resin, it is
selected from the above-mentioned exemplary polyamide resin or the
precursor thereof, the polyamide imide resin or the precursor
thereof, or the polyamide resin and used. Incidentally, the
respective precursor may be a partially imidated polyamic acid
resin.
That is, (B'') the heat-resistant resin B'' is used selected from
fine particles which are insoluble in (C'') the solvent of the
heat-resistant paste according to the present invention before
heating and drying.
Examples of such (B'') a heat-resistant resin B'' (including a
combination with the solvent) may include those resins as disclosed
in Table 1 specifically exemplified as (II) heat-resistant resins B
in Japanese Provisional Patent Publication No. 246777/1999, a
polyamic acid (the solvent is .gamma.-butyrolactone) of
3,4,3',4'-benzophenone tetracarboxylic acid
dianhydride/4,4'-diaminodiphenyl ether (1/1; molar ratio), a
polyamic acid (the solvent is .gamma.-butyrolactone) of
3,3',4,4'-biphenyltetracarboxylic acid
dianhydride/3,4,3',4'-benzophenone tetracarboxylic acid
dianhydride/4,4'-diaminodiphenyl ether (0.5/0.5/1; molar ratio),
etc. These are one example showing an embodiment of the present
invention and the invention is not specifically limited by
these.
When stability of (C'') the solvent, and solubility and
productivity of (B'') the heat-resistant resin B'' to (C'') the
solvent are considered, a combination of (B'') the heat-resistant
resin B'' comprising an aromatic polyimide resin obtained by
reacting an aromatic tetracarboxylic acid dianhydride containing 50
mol % or more of 3,4,3',4'-benzophenonetetracarboxylic acid
dianhydride and an aromatic diamine containing 50 mol % or more of
4,4'-diaminodiphenyl ether, and (C'') the solvent of
.gamma.-butyrolactone is preferred.
A heating and drying temperature of the heat-resistant resin paste
according to the above-mentioned combination is usually 50 to
350.degree. C., and within this range, it is preferred to raising
the temperature from a low temperature to a high temperature
stepwisely.
Also, (B'') the heat-resistant resin B'' and (A'') the
heat-resistant resin A'' are preferably used those having
compatibility. More specifically, a difference of solubility
parameters between (B'') the heat-resistant resin B'' and (A'') the
heat-resistant resin A'' of preferably 2.0 or less, more preferably
1.5 or less is used in combination. Here, the solubility parameter
is a value [unit: (MJ/m.sup.3).sup.1/2] calculated according to the
system of Fedors described in Polym. Eng. Sci., Vol. 14, pp. 147
154.
As the tetracarboxylic acid dianhydride to be used for preparation
of the heat-resistant resin of the present invention, there may be
mentioned, for example, pyromellitic acid dianhydride,
3,3',4,4'-biphenyltetracarboxylic acid dianhydride,
2,2',3,3'-biphenyltetracarboxylic acid dianhydride,
2,3,3',4'-biphenyltetracarboxylic acid dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
bis(2,3-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)sulfone dianhydride,
3,4,9,10-perylenetetracarboxylic acid dianhydride,
bis(3,4-dicarboxyphenyl)ether dianhydride,
benzene-1,2,3,4-tetracarboxylic acid dianhydride,
3,4,3',4'-benzophenonetetracarboxylic acid dianhydride,
2,3,2',3'-benzophenonetetracarboxylic acid dianhydride,
2,3,3',4'-benzophenonetetracarboxylic acid dianhydride,
1,2,5,6-naphthalenetetracarboxylic acid dianhydride,
2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
1,2,4,5-naphthalenetetracarboxylic acid dianhydride,
1,4,5,8-naphthalenetetracarboxylic acid dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride,
2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride,
2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid
dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid
dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride,
bis(3,4-dicarboxyphenyl)methylphenylsilane dianhydride,
bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride,
1,4-bis(3,4-dicarboxyphenyldimethylsilyl)benzene dianhydride,
1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane
dianhydride, p-phenylbis(trimellitic acid monoester acid
anhydride), 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane
dianhydride,
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane
dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane
dianhydride, 4,4-bis(3,4-dicarboxyphenoxy)diphenylsulfide
dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzene
bis(trimellitic anhydride),
1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic
anhydride), 1,2-(ethylene)bis(trimellitate dianhydride),
1,3-(trimethylene)bis(trimellitate dianhydride),
1,4-(tetramethylene)bis(trimellitate dianhydride),
1,5-(pentamethylene)bis(trimellitate dianhydride),
1,6-(hexamethylene)bis(trimellitate dianhydride),
1,7-(heptamethylene)bis(trimellitate dianhydride),
1,8-(octamethylene)bis(trimellitate dianhydride),
1,9-(nonamethylene)bis(trimellitate dianhydride),
1,10-(decamethylene)bis(trimellitate dianhydride),
1,12-(dodecamethylene)bis(trimellitate dianhydride),
1,16-(hexadecamethylene)bis(trimellitate dianhydride),
1,18-(octadecamethylene)bis(trimellitate dianhydride), etc. These
compounds may be used alone or in combination of two or more
kinds.
In the above-mentioned aromatic tetracarboxylic acid, a
tetracarboxylic acid dianhydride other than the aromatic
tetracarboxylic acid dianhydride may be used in the range not
exceeding 50 mol % of the aromatic tetracarboxylic acid depending
on the purpose.
Such a tetracarboxylic acid dianhydride may include, for example,
tetraethylene carboxylic acid dianhydride,
1,2,3,4-butanetetracarboxylic acid dianhydride,
pyrazine-2,3,5,6-tetracarboxylic acid dianhydride,
thiophene-2,3,4,5-tetracarboxylic acid dianhydride,
decahydronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride,
4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic
acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic acid
dianhydride, pyrrolidone-2,3,4,5-tetracarboxylic acid dianhydride,
1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,
bis(exo-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid dianhydride,
bicyclo[2.2.2]oct(7)-ene-2,3,5,6-tetracarboxylic acid dianhydride,
5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic
acid anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid
dianhydride, etc.
As the acid anhydride to be used in (A'') the heat-resistant resin
A'' to be used in the present invention, in the viewpoints that a
resin film is to be obtained at a relatively low drying temperature
without impairing heat-resistance, a trimellitate including
1,4-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic
anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene
bis(trimellitic anhydride), 1,2-(ethylene)bis(trimellitate
dianhydride), 1,3-(trimethylene)bis(trimellitate dianhydride),
1,4-(tetramethylene)bis(trimellitate dianhydride),
1,5-(pentamethylene)bis(trimellitate dianhydride),
1,6-(hexamethylene)bis(trimellitate dianhydride),
1,7-(heptamethylene)bis(trimellitate dianhydride),
1,8-(octamethylene)bis(trimellitate dianhydride),
1,9-(nonamethylene)bis(trimellitate dianhydride),
1,10-(decamethylene)bis(trimellitate dianhydride),
1,12-(dodecamethylene)bis(trimellitate dianhydride),
1,16-(hexadecamethylene)bis(trimellitate dianhydride),
1,18-(octadecamethylene)bis(trimellitate dianhydride), etc. is
preferably used.
As the aromatic diamine, there may be mentioned, for example,
o-phenylenediamine, m-phenylenediamine, p-phenylenediamine,
3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
3,3'-diaminodiphenyldifluoromethane,
4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone,
3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide,
4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone,
2,2-bis(3-aminophenyl)propane, 2,2-bis(3,4-diaminophenyl)propane,
2,2-bis(4-aminophenyl)propane,
2,2-bis(3-aminophenyl)hexafluoropropane,
2,2-bis(3,4-diaminophenyl)hexafluoropropane,
2,2-bis(4-aminophenyl)hexafluoropropane,
1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene,
3,3'-[1,4-phenylenebis(1-methylethylidene)]bisaniline,
3,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline,
4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline,
2,2-bis[4-(3-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane,
2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,
bis[4-(3-aminophenoxy)phenyl]sulfide,
bis[4-(4-aminophenoxy)phenyl]sulfide,
bis[4-(3-aminophenoxy)phenyl]sulfone,
bis[4-(4-aminophenoxy)phenyl]sulfone, 1,2-diamino-4-carboxybenzene,
1,3-diamino-5-carboxybenzene, 1,3-diamino-4-carboxybenzene,
1,4-diamino-5-carboxybenzene, 1,5-diamino-6-carboxybenzene,
1,3-diamino-4,6-dicarboxybenzene, 1,2-diamino-3,5-dicarboxybenzene,
4-(3,5-diaminophenoxy)benzoic acid, 3-(3,5-diaminophenoxy)benzoic
acid, 2-(3,5-diaminophenoxy)benzoic acid,
3,3'-dicarboxy-4,4'-diaminobiphenyl,
3,3'-diamino-4,4'-dicarboxybiphenyl,
2,2-bis(4-carboxy-3-aminophenyl)propane,
2,2-bis(4-carboxy-3-aminophenyl)hexafluoropropane,
bis(4-carboxy-3-aminophenyl)ketone,
bis(4-carboxy-3-aminophenyl)sulfide,
bis(4-carboxy-3-aminophenyl)ether,
bis(4-carboxy-3-aminophenyl)sulfone,
bis(4-carboxy-3-aminophenyl)methane,
4-[(2,4-diamino-5-pyrimidinyl)methyl]benzoic acid,
p-(3,6-diamino-s-triazin-2-yl)benzoic acid,
2,2-bis(4-amino-3-carboxyphenyl)propane,
2,2-bis(4-amino-3-carboxyphenyl)hexafluoropropane,
bis(4-amino-3-carboxyphenyl)ketone,
bis(4-amino-3-carboxyphenyl)sulfide,
bis(4-amino-3-carboxyphenyl)ether,
bis(4-amino-3-carboxyphenyl)sulfone,
bis-(4-amino-3-carboxyphenyl)methane,
bis(4-amino-3-carboxyphenyl)difluoroemethane,
1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene,
1,3-diamino-4-hydroxybenzene, 1,4-diamino-6-hydroxybenzene,
1,5-diamino-6-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene,
1,2-diamino-3,5-dihydroxybenzene, 4-(3,5-diaminophenoxy)phenol,
3-(3,5-diaminophenoxy)phenol, 2-(3,5-diaminophenoxy)phenol,
3,3'-dihydroxy-4,4'-diaminobiphenyl,
3,3'-diamino-4,4'-dihydroxybiphenyl,
2,2-bis(4-hydroxy-3-aminophenyl)propane,
2,2-bis(4-hydroxy-3-aminophenyl)hexafluoropropane,
bis(4-hydroxy3-aminophenyl)ketone,
bis(4-hydroxy-3-aminophenyl)sulfide,
bis(4-hydroxy-3-aminophenyl)ether,
bis(4-hydroxy-3-aminophenyl)sulfone,
bis(4-hydroxy-3-aminophenyl)methane,
4-[(2,4-diamino-5-pyrimidinyl)methyl]phenol,
p-(3,6-diamino-s-triazin-2-yl)phenol,
bis(4-hydroxy-3-aminophenyl)difluoromethane,
2,2-bis(4-amino-3-hydroxyphenyl)propane,
2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane,
bis(4-amino-3-hydroxyphenyl)ketone,
bis(4-amino-3-hydroxyphenyl)sulfide,
bis(4-amino-3-hydroxyphenyl)ether,
bis(4-amino-3-hydroxyphenyl)sulfone,
bis(4-amino-3-hydroxyphenyl)methane,
bis(4-amino-3-hydroxyphenyl)difluoromethane,
##STR00009## etc., and the above-mentioned aromatic diamine may be
used in combination of two or more kinds.
For producing the polyimide type resin, as the diamine compound
other than the above-mentioned aromatic diamines, a diamine
compound including an aliphatic diamine such as 1,2-diaminoethane,
1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane,
1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane,
1,3-bis(3-aminopropyl)tetramethyldisiloxane,
1,3-bis(3-aminopropyl)tetramethylpolysiloxane, etc., and
diaminosiloxane, etc. may be used. In the viewpoint of
heat-resistance, an amount of these diamines is preferably 50% by
weight or less based on the total amount of the diamine
compound.
In the preparation of the polyimide resin to be used in the present
invention, the aromatic tetracarboxylic acid dianhydride and the
diamine compound are preferably reacted by using substantially the
same molar amounts in the point of the film property.
To make control of the end point of the reaction easy and to obtain
a polyimide resin having a desired molecular weight, it is
preferred to use either of the acid component or the amine
component with a slightly excess amount (1.01 to 1.10 or so) in
formulation molar amount. Or else, as a terminal sealing agent for
the acid component or the amine component, there may be added, for
example, a tricarboxylic acid monoanhydride such as maleic
anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc.,
or a monoamine such as aniline, benzylamine, etc., in an amount of
0.01 to 0.10 mol per mole of either of the components of the acid
component or the amine component.
A molecular weight of the polyimide resin to be used in the present
invention is preferably in a number average molecular weight of
5,000 to 80,000. If it is less than 5,000, mechanical properties
tend to be lowered, while if it exceeds 80,000, a viscosity of the
reaction mixture during the synthesis thereof becomes too high so
that workability tends to be lowered.
The number average molecular weight is a calculated value based on
the molecular weight of standard polystyrene obtained from the gel
permeation chromatography method using a calibration curve of
polystyrenes the molecular weights of which had been known. For
example, it can be measured by the following conditions. The values
in Examples mentioned hereinbelow are measured by the following
conditions. Device: Hitachi Type 655A Column: Gelpak GL-S300, MDT-S
(300 mm.times.8 mm.phi.), 2 columns, manufactured by Hitachi
Chemical Co., Ltd. Eluent: Tetrahydrofuran/dimethylformamide=1/1
(volume), H.sub.3PO.sub.4 (0.06 mol/liter)/LiBr.H.sub.2O (0.03
mol/liter) Flow amount: 1 ml/min Detector: UV (270 nm)
The reaction of the aromatic tetracarboxylic acid dianhydride and
the diamine compound is carried out in an organic solvent. As the
organic solvent, there may be mentioned, for example, a
nitrogen-containing compound such as N-methylpyrrolidone,
dimethylacetamide, dimethylformamide,
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone,
1,3-dimethyl-2-imidazolidinone, etc.; a sulfur compound such as
sulforane, dimethylsulfoxide, etc.; a lactone such as
.gamma.-butyrolactone, .gamma.-valerolactone, .gamma.-caprolactone,
.gamma.-heptalactone, .alpha.-acetyl-.gamma.-butyrolactone,
.epsilon.-caprolactone, etc.; an ether such as dioxane,
1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, triethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, tetraethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, etc.; a ketone such as methyl ethyl
ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc.;
an alcohol such as butanol, octyl alcohol, ethylene glycol,
glycerin, diethylene glycol monomethyl (or monoethyl)ether,
triethylene glycol monomethyl (or monoethyl)ether, tetraethylene
glycol monomethyl (or monoethyl)ether, etc.; a phenol such as
phenol, cresol, xylenol, etc.; an ester such as ethyl acetate,
butyl acetate, ethyl cellosolve acetate ("cellosolve" is trade
name), butyl cellosolve acetate ("cellosolve" is trade name), etc.,
a hydrocarbon such as toluene, xylene, diethylbenzene, cyclohexane,
etc.; a halogenated hydrocarbon such as trichloroethane,
tetrachloroethane, monochlorobenzene, etc.
These organic solvents are used alone or in combination of two or
more kinds. When solubility, low hygroscopic property, low
temperature curing property and environmental safety, etc., are
considered, it is preferred to use a lactone, an ether or a
ketone.
A reaction temperature is usually 80.degree. C. or less, preferably
0 to 60.degree. C. In progress with the reaction, a viscosity of
the reaction mixture gradually increases. In this case, a polyamic
acid which is a precursor of the polyimide resin is formed.
The polyimide resin can be also obtained by subjecting the
above-mentioned reaction product (the polyimide precursor) to
dehydration and cyclization. The dehydration and cyclization can be
carried out by the method of subjecting to heat treatment at
120.degree. C. to 250.degree. C. (heat imidation) or the method of
using a dehydrating agent (chemical imidation). In the case of the
method of subjecting to heat treatment at 120.degree. C. to
250.degree. C., it is preferably carried out by removing water
generated by the dehydration reaction out of the system. At this
time, water may be removed by azeotropic distillation by using
benzene, toluene, xylene, etc.
In the method of subjecting to dehydration and cyclization by using
a dehydrating agent, a carbodiimide compound such as
dicyclohexylcarbodiimide, etc., is preferably used. At this time,
if necessary, a dehydrating catalyst such as pyridine,
isoquinoline, trimethylamine, aminopyridine, imidazole, etc., may
be used. The dehydrating agent or the dehydrating catalyst is
preferably used in an amount in the range of each 1 to 8 mol based
on 1 mol of the aromatic tetracarboxylic acid dianhydride.
To reduce the number of production steps and to heighten economical
merit, the method of subjecting to heat treatment at 120.degree. C.
to 250.degree. C. (heat imidation) is preferred.
The polyamide imide resin or a precursor thereof in the present
invention can be produced by using a trivalent tricarboxylic acid
anhydride or a derivative thereof such as a trimellitic acid
anhydride derivative including trimellitic anhydride or a chloride
of the trimellitic anhydride, etc., in place of part or whole part
of the aromatic tetracarboxylic acid dianhydride in the production
of the above-mentioned polyimide resin or a precursor thereof.
Also, it can be produced by using an aromatic diisocyanate in place
of the aromatic diamine. As the aromatic diisocyanate which can be
used, a compound obtained by reacting the above-mentioned aromatic
diamine and phosgene or thionyl chloride.
Also, as the polyamide imide resin in the present invention, a
polyamide imide resin obtained by reacting an aromatic
tetracarboxylic aciddianhydride and a diamine compound containing
dihydrazide isophthalate as an essential component is preferably
used. As the aromatic tetracarboxylic acid and the diamine compound
other than dihydrazide isophthalate, those as mentioned above may
be used. A ratio of the diamine compound in the dihydrazide
isophthalate is preferably 1 to 100 mol %. If it is less than 1 mol
%, when the resin paste of the present invention is used as an
adhesive of a semiconductor device, solvent resistance to an
encapsulating agent tends to be lowered, while if an amount of the
dihydrazide isophthalate is too much, humidity resistance of an
adhesive layer formed by the resin paste of the present invention
tends to be lowered. Thus, it is preferably 10 to 80 mol %,
particularly preferably 20 to 70 mol %. This polyamide imide resin
can be obtained by the same method as those of the synthesis of the
above-mentioned polyimide resin under the conditions such as the
formulation ratio of the aromatic tetracarboxylic acid dianhydride
and the diamine compound, the organic solvent to be used and the
synthesis method, etc.
The polyamide resin in the present invention can be produced by
reacting the aromatic dicarboxylic acid such as terephthalic acid,
isophthalic acid, phthalic acid, etc., a derivative thereof such as
dichloride, anhydride, etc., and the aromatic diamine or aromatic
diisocyanate with the formulation as mentioned above.
As the solvent (C'') to be used in the present invention, solvents
described in, for example "Solvent Handbook" (published by
Kodansha, published in 1976), pp. 143 852, can be used.
As the organic solvent, there may be mentioned, for example, a
nitrogen-containing compound such as N-methylpyrrolidone,
dimethylacetamide, dimethylformamide,
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone,
1,3-dimethyl-2-imidazolidinone, etc.; a sulfur compound such as
sulforane, dimethylsulfoxide, etc.; a lactone such as
.gamma.-butyrolactone, .gamma.-valerolactone, .gamma.-caprolactone,
.gamma.-heptalactone, .alpha.-acetyl-.gamma.-butyrolactone,
.epsilon.-caprolactone, etc.; an ether such as dioxane,
1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, triethyleneglycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, tetraethyleneglycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, etc.; a carbonate such as ethylene
carbonate, propylene carbonate, etc.; a ketone such as methyl ethyl
ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc.;
an alcohol such as butanol, octyl alcohol, ethylene glycol,
glycerin, diethylene glycol monomethyl (or monoethyl)ether,
triethylene glycol monomethyl (or monoethyl)ether, tetraethylene
glycol monomethyl (or monoethyl)ether, etc.; a phenol such as
phenol, cresol, xylenol, etc.; an ester such as ethyl acetate,
butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate,
etc., a hydrocarbon such as toluene, xylene, diethylbenzene,
cyclohexane, etc.; a halogenated hydrocarbon such as
trichloroethane, tetrachloroethane, monochlorobenzene, etc. These
solvents may be used alone or in combination.
The boiling point of (C'') the solvent is preferably 100.degree. C.
or higher, particularly preferably 150 to 300.degree. C. when a
usable time of a paste at the time of effecting screen printing is
considered.
Also, when stability to hygroscopicity of a paste is considered,
(C'') the solvent preferably used is a lactone such as
.gamma.-butyrolactone, .gamma.-valerolactone, .gamma.-caprolactone,
.gamma.-heptalactone, .alpha.-acetyl-.gamma.-butyrolactone,
.epsilon.-caprolactone, etc.; an ether such as dioxane,
1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, triethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, tetraethylene glycol dimethyl (or diethyl,
dipropyl, dibutyl)ether, etc.; a carbonate such as ethylene
carbonate, propylene carbonate, etc.; a ketone such as methyl ethyl
ketone, methyl isobutyl ketone, cyclohexanone, acetophenone,
etc.
The heat-resistant paste of the present invention can be prepared
by, for example, mixing the heat-resistant resin A'' of (A''), the
heat-resistant resin B'' of (B'') and the solvent of (C''), heating
the mixture to dissolve the resins and cooling the solution,
whereby fine particles of the heat-resistant resin B'' of (B'') are
precipitated and dispersed in the solvent of (C'').
A temperature at the time of heating and dissolution, it is not
particularly limited so long as the mixture of the heat-resistant
resin A'' of (A''), the heat-resistant resin B'' of (B'') and the
solvent of (C'') becomes substantially uniform and transparent
solution, and is generally 40.degree. C. to 250.degree. C. under
stirring. A time required for the dissolution is optional and
preferably 0.1 to 5 hours, more preferably 1 to 5 hours.
Then, the conditions for cooling the solution dissolved by heating
are not specifically limited so long as the heat-resistant resin
B'' of (B'') becomes fine particles in the mixed solution of the
heat-resistant resin A'' of (A'') and the solvent of (C'') and
precipitates and disperses therein. It is generally -20.degree. C.
to 100.degree. C. which is less than the temperature at dissolution
under heating, and the procedure is preferably carried out under
the conditions of stirring or allowed to stand for one hour to 60
days. As the cooling conditions to make fine particles within a
short period of time, it is preferably carried out under the
conditions of stirring at a constant temperature between 0.degree.
C. to 80.degree. C. and allowed to stand for 5 to 80 hours. A rate
of cooling from the temperature at which the mixture is dissolved
under heating to cool to -20.degree. C. to 100.degree. C. is
optional but rapid cooling likely causes aggregation of the
precipitating fine particles so that it is, in general, preferably
carried out, under stirring, by cooing at a rate of 0.1 to
10.degree. C./min. A production atmosphere is preferably an inert
gas atmosphere such as a dried nitrogen gas, etc.
Also, the heat-resistant resin paste of the present invention can
be produced by, for example, charging starting materials
constituting the heat-resistant resin B'' of (B'') in a mixed
solution of the heat-resistant resin A'' of (A'') and the solvent
of (C''), after dissolving the resin, reacting the materials in the
solution of the heat-resistant resin A'' of (A'') and the solvent
of (C'') at a temperature at which the heat-resistant resin B'' of
(B'') is not precipitated to synthesize the heat-resistant resin
B'' of (B''), and then, cooling the mixture to precipitate and
disperse the heat-resistant resin B'' of (B'') in the solution of
the heat-resistant resin A'' of (A'') and the solvent of (C''). As
the starting materials constituting the heat-resistant resin B'' of
(B''), the above-mentioned materials can be used.
Also, the heat-resistant resin paste of the present invention can
be produced by, for example, charging starting materials
constituting the heat-resistant resin A'' of (A'') in a mixed
solution of the heat-resistant resin B'' of (B'') and the solvent
of (C''), after dissolving the resin, reacting the materials in the
solution of the heat-resistant resin B'' of (B'') and the solvent
of (C'') at a temperature at which the heat-resistant resin A'' of
(A'') is not precipitated to synthesize the heat-resistant resin
A'' of (A''), and then, cooling the mixture to precipitate and
disperse the heat-resistant resin B'' of (B'') in the solution of
the heat-resistant resin A'' of (A'') and the solvent of (C''). As
the starting materials constituting the heat-resistant resin A'' of
(A''), the above-mentioned materials can be used.
(D) The particle or liquid material having rubber elasticity of the
present invention is not particularly limited so long as it is
particles or a liquid material having rubber elasticity, and there
may be mentioned particles or a liquid material having rubber
elasticity such as acrylic rubber, fluorine rubber, silicone
rubber, butadiene rubber, etc. Of these, particles having rubber
elasticity mainly comprising silicone rubber are preferably
used.
These rubber elastomers are preferably fine particles with sphere
or amorphous shape having an average particle size of 0.1 to 50
.mu.m. The average particle size can be measured by an electron
microscopic method, particle analyzer method, etc. If the average
particle size is less than 0.1 .mu.m, aggregation between particles
occurs, sufficient dispersion cannot be carried out and stability
of the paste with a lapse of time tends to be lowered. Also, if it
exceeds 50 .mu.m, the surface of the coated film becomes rough and
a uniform coated film cannot be obtained.
The surface of the particles having rubber elasticity to be used in
the present invention may be the rubber elastic material itself,
that coated by a resin, and preferably that chemically modified by
a functional group such as an epoxy group, etc. A material which is
chemically modified by a functional group such as an amino group,
an acrylic group, a phenyl group, etc., in place of the
above-mentioned epoxy group may be used. By adding these particles
having rubber elasticity to the heat-resistant resin, it is
possible to control a modulus of elasticity without impairing
heat-resistance and adhesiveness of the resin.
The particles having rubber elasticity are commercially available
from Dow Corning Toray Silicone Co., Ltd., Japan under the trade
names of TREFIL E-601, TREFIL E-600, etc., Shin-Etsu Chemical
Industry, Japan, under the trade names of Silicone rubber powder
KMP594, KMP598, etc., and Silicone complex powder KMP600, KMP605,
etc.
Also, in the present invention, the resin film obtained from the
heat-resistant resin paste can be optionally controlled the modulus
of elasticity thereof in the range of 0.2 to 3.0 GPa, and the
heat-resistant resin paste preferably has the modulus of elasticity
at 150.degree. C. of 10 to 100% to that at -65.degree. C. If it
exceeds 3.0 GPa, stress relaxation becomes insufficient and crack,
etc, occurs at the connecting portion of solder, etc. whereby
reliability tends to be impaired, while if it is less than 0.2 GPa,
a wiring layer tends to be broken by strain. If the modulus of
elasticity at 150.degree. C. is less than 10% to that at
-65.degree. C., strain likely occurs at solder ball connecting
portion, etc. by the cold-heat impact cycle test whereby
reliability is lowered.
Also, in the present invention, the resin film obtained from the
heat-resistant resin paste has a glass transition temperature of
180.degree. C. or higher, and the heat-resistant resin paste
preferably has a 5% weight loss temperature of 300.degree. C. or
higher. If the glass transition temperature is less than
180.degree. C., or the 5% weight loss temperature is less than
300.degree. C., the resin tends to be decomposed in the sputtering
step, etc.
Also, in the present invention, the heat-resistant resin paste
preferably has a viscosity of 10 to 1,000 Pas, and a thixotropic
coefficient of 1.2 or higher.
By making the thixotropic coefficient to 1.2 or higher, good screen
printing property can be obtained. If the thixotropic coefficient
is less than 1.2, sufficient printing property or resolution can be
difficultly obtained. The thixotropic coefficient is more
preferably 2.0 to 10.0. If it exceeds 10.0, a formed pattern tends
to cause thin spot.
Also, the viscosity is preferably made 10 Pas to 1,000 Pas. If it
is less than 10 Pas, sufficient film thickness and resolution can
be difficultly obtained, while if it exceeds 1,000 Pas, workability
at the time of forming a pattern tends to be lowered. It is more
preferably 50 Pas to 700 Pas, particularly preferably 100 Pas to
600 Pas. Here, the thixotropic coefficient is measured by using an
E type viscometer (manufactured by TOKIMEC INC., Japan, Type EHD-U)
with a sample amount of 0.4 g and a measurement temperature of
25.degree. C. It is shown by a ratio of an apparent viscosity
.eta.1 at a rotation number of 1 min.sup.-1 and .eta.10 at a
rotation number of 10 min.sup.-1, .eta.1/.eta.10. The viscosity is
shown by an apparent viscosity .eta.0.5 at a rotation number of 0.5
min.sup.-1. The viscosity can be controlled by, for example, a
solid component concentration of the resin past and an amount of
(B'') the heat-resistant resin B''. When these values are larger,
the viscosity also become higher.
In the present invention, the modulus of elasticity of the resin
film obtained by combining (A'') the heat-resistant resin A'' which
is soluble in a solvent at room temperature and a temperature at
the time of heating and drying, (B'') the heat-resistant resin B''
which does not dissolve in a solvent at room temperature but
dissolve at a temperature at the time of heating and drying, and
(D) particles or a liquid material D showing rubber elasticity can
be controlled optionally in the range of 0.2 to 3.0 GPa and the
modulus of elasticity at 150.degree. C. can be made a size of 10 to
100% that at -65.degree. C.
Moreover, the resin film obtained by the heat-resistant resin paste
of the present invention has a glass transition temperature of
180.degree. C. or higher, and a 5% weight loss temperature of
300.degree. C. or higher so that it has excellent resistances to
the processes such as sputtering, plate resist formation,
electroplating or electroless plating, resist removal, thin film
metal etching, solvent treatment, solder ball mounting, etc. which
are used when preparing a semiconductor device.
A formulation ratio of the heat-resistant resin A'' of (A''), the
heat-resistant resin B'' of (B''), the solvent of (C'') and the
particles or liquid material showing rubber elasticity of (D) is
preferably, based on 100 parts by weight of the heat-resistant
resin A'' of (A''), 10 to 300 parts by weight of the heat-resistant
resin B'' of (B''), 100 to 3,000 parts by weight of the solvent of
(C''), and 10 to 700 parts by weight of the particles or liquid
material showing rubber elasticity of (D), more preferably 20 to
200 parts by weight of the heat-resistant resin B'' of (B''), 150
to 2,000 parts by weight of the solvent of (C''), and 20 to 400
parts by weight of the particles or liquid material showing rubber
elasticity of (D), and particularly preferably 20 to 200 parts by
weight of the heat-resistant resin B'' of (B''), 200 to 1,000 parts
by weight of the solvent of (C''), and 20 to 200 parts by weight of
the particles or liquid material showing rubber elasticity of
(D).
If the amount of the heat-resistant resin B'' of (B'') is less than
10 parts by weight, thixotropic property is insufficient at the
time of forming a pattern by screen printing or dispense, etc., and
resolution tends to be lowered. Also, if it exceeds 300 parts by
weight, fluidity of the paste is impaired so that printing property
or dispense property tends to be lowered.
If the amount of the solvent of (C'') is less than 100 parts by
weight, fluidity of the paste is impaired so that printing property
or dispense property tends to be lowered. Also, if it exceeds 3,000
parts by weight, a viscosity of the paste becomes low so that
formation of a thick film becomes difficult whereby resolution
tends to be impaired.
If the amount of the particles or liquid material showing rubber
elasticity of (D) is less than 5 parts by weight, elasticity of the
heat-resistant resin film becomes high and stress-releasing
capability tends to be impaired. Also, if an amount of the
particles or liquid material showing rubber elasticity of (D)
exceeds 700 parts by weight, mechanical properties of the coated
film is lowered so that a function as the coated film tends to be
lowered.
The heat-resistant resin paste of the present invention can be
prepared, if desired, by making a paste in which fine particles of
the heat-resistant resin B'' of (B'') are dispersed in the solution
of the heat-resistant resin A'' of (A'') and the solvent of (C''),
and then, adding 1 to 30 parts by weight of a cross-linking agent
having a functional group capable of bonding to a hydroxyl group or
a carboxyl group based on the total amount of the heat resistant
resin paste as 100 parts by weight.
As the a cross-linking agent having a functional group capable of
bonding to a hydroxyl group or a carboxyl group, preferably used is
a material having two or more functional groups in the molecule, at
least one of which reacts with the heat-resistant resin having the
hydroxyl group or carboxyl group in the molecular main chain and
the remaining functional groups react with the heat-resistant resin
having the hydroxyl group or carboxyl group in the molecular main
chain or react with the other functional group. The molecular
structure or the molecular weight, etc., are not specifically
limited so long as it has two or more functional groups.
As the functional group reactive with the hydroxyl group, there may
be mentioned, for example, an epoxy resin, an isocyanate group, a
methylol group, etc. As the functional group reactive with the
carboxyl group, there may be mentioned, for example, an epoxy
group, an amino group, a vinyl group, an oxazoline group, an
ethoxysialne group, etc. A coupling agent which can give gentle
cross-linking structure to the cured product of the heat-resistant
resin paste and excellent in preservation stability to the
heat-resistant resin paste is preferably used. As the coupling
agent, there may be mentioned, for example, a silane coupling
agent, a titanate type coupling agent, an aluminum type coupling
agent, etc. Of these, a silane coupling agent is preferably
used.
As the silane coupling agent, there may be mentioned, for example,
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane,
.gamma.-anilinopropyltrimethoxysilane, vinyltrimethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-ureidopropyltriethoxysilane,
.gamma.-methacryloxypropylmethylenedimethoxysilane, etc.
A silane coupling agent having an epoxy group and a methoxysilane
group in the molecule is preferably used to the heat-resistant
resin having a hydroxyl group in the molecule, more preferably
.gamma.-glycidoxypropyltrimethoxysilane is used. In the
heat-resistant resin paste obtained by such a combination, its
curing product by heating has a gentle cross-linking structure so
that when it is used for a resin encapsulation type semiconductor
device, it is not melted by a encapsulating material-constituting
resin under a molding temperature whereby it is excellent in solder
resistant reflow property.
In the present invention, the aromatic thermoplastic resin which is
insoluble in a polar solvent at room temperature but is soluble
under heating gives thixotropy to the resin composition whereby a
precise pattern can be formed by a screen printing and dispense
coating.
In the present invention, it is preferred that a modulus of
elasticity at 25.degree. C. can be controlled in the range of 0.2
to 3.0 GPa, and the modulus of elasticity at 150.degree. C. is in
the range of 10 to 100% to that at -65.degree. C.
In the present invention, a glass transition temperature (Tg) is
preferably 180.degree. C. or higher and a thermal decomposition
temperature is preferably 300.degree. C. or higher.
In the resin composition of the present invention, it is preferred
that a viscosity is within the range of 1 to 1000 Pas, a
thixotropic coefficient is 1.2 or more and a precise pattern can be
formed.
If the viscosity of the resin composition is less than 1 Pas, a
shape of the resin composition at printing cannot be maintained,
and stringing of the resin composition becomes remarkable whereby
printing is difficult. Also, if it exceeds 1000 Pas, the resin
composition becomes hard and handling at printing becomes extremely
difficult and there is a problem that formation of a precise
pattern becomes difficult. Also, the thixotropic coefficient is
preferably within the range of 1.2 to 20, more preferably in the
range of 1.5 to 15. If the thixotropic coefficient is less than
1.2, even when a precise pattern is formed, the shape is
degenerated whereby formation of a precise pattern tends to be
difficultly formed.
A method of obtaining a precise pattern by the resin composition of
the present invention and a method of obtaining a resin film
pattern using the heat-resistant resin paste of the same are not
specifically limited, and, there may be mentioned, for example,
screen printing method, dispense coating method, potting method,
curtain coating method, letterpress printing method, intaglio
printing method, lithographic printing method, etc.
A semiconductor device using the resin composition of the present
invention or a semiconductor device using a resin film obtained
from the heat-resistant resin paste of the same can be obtained by
coating or adhering the resin composition or the heat-resistant
resin paste of the present invention to a substrate or a lead
frame, and adhering a chip. For example, it can be produced by
coating the resin composition or the heat-resistant resin paste of
the present invention on the surface of a semiconductor part and
drying it to form a protective film. After coating or adhering the
resin composition or the heat-resistant resin paste of the present
invention on the surface of a chip, it may be adhered to the
substrate or the lead frame. Coating and drying can be carried out
by the conventionally known methods. At this time, a coated film
can be obtained only by a step of heating at 250.degree. C. or
lower or a step of drying a solvent at 250.degree. C. or lower
without accompanying imidation. A glass transition temperature of
the formed coated film is 180.degree. C. or higher and a thermal
decomposition temperature is 300.degree. C. or higher so that it
has sufficient heat resistance. Also, the modulus of elasticity of
the coated film can be controlled within the range of 0.2 to 3.0
GPa so that it can be applied to any kinds of semiconductor
devices.
A semiconductor device using the resin composition or the
heat-resistant resin paste of the present invention can be produced
by the steps of forming at least one resin layer by coating the
resin composition or the heat-resistant resin paste of the present
invention on a semiconductor substrate on which a plural number of
wirings with the same structure have been formed and drying to form
at least one resin layer; forming re-wiring on the resin layer
which is electrically connected to an electrode on the
semiconductor substrate; forming a protective layer on the
re-wiring; forming an outer electrode terminal to the protective
layer; and then, subjecting to dicing, if necessary.
A substrate for the above semiconductor device is not particularly
limited, and there may be mentioned, for example, a silicon wafer
on which a memory circuit is formed, a silicon wafer on which a
logic circuit is formed, etc. A coating method of the
above-mentioned resin layer is not particularly limited and screen
printing or dispense coating is preferred.
In the present invention, a drying method of the resin layer can be
carried out by the conventionally known method. At this time, a
resin layer can be obtained only by a heating step at 250.degree.
C. or lower or by a drying step of a solvent at 250.degree. C. or
lower without accompanying with imidation. According to this
procedure, a resin layer can be formed on a substrate on which a
wiring is formed without causing any damage. It is preferred to
have heat resistance that a glass transition temperature Tg of the
formed resin layer is 180.degree. C. or higher and a thermal
decomposition temperature is 300.degree. C. or higher. Also, a 5%
weight loss temperature is 300.degree. C. or higher and it has
sufficient heat-resistance. Moreover, it has sputtering resistance,
plating resistance, alkali resistance, etc., which are required in
the step of forming re-wiring. Since a modulus of elasticity of the
resin layer can be optionally controlled in the range of 0.2 to 3.0
GPa, so that it can be applied to any kinds of semiconductor
devices. Accordingly, a warpage amount of a silicon wafer can be
reduced. A semiconductor device produced by this method is expected
to be improved in yield and it is possible to improve
productivity.
Next, the resin for insulating a semiconductor, the semiconductor
device using the same and the process for producing the same will
be explained.
The method of producing a semiconductor device according to the
present invention comprises a step of forming a plural number of
resin layers on a semiconductor substrate on which a wiring
(pattern) has been formed; a step of forming, on the resin layer, a
second wiring layer electrically connected to an electrode on the
semiconductor substrate; a step of forming a protective layer on
the second wiring layer except for a portion to which an outer
electrode terminal is mounted; and a step of forming the outer
electrode terminal on the second wiring layer.
The method of producing a semiconductor device according to the
present invention also comprise a step of forming a resin layer on
a semiconductor substrate on which a first wiring layer has been
formed; a step of providing a through hole (s) at part of the resin
layer penetrating to the first wiring layer; and a step of forming
a second wiring layer on the resin layer by which an outer
connection terminal and the first wiring layer are electrically
connected to each other.
The method of producing a semiconductor device according to the
present invention further comprise a step of forming a plural
number of resin layers on a semiconductor wafer on which an
electronic circuit (a first wiring layer) has been formed by
printing a resin having an elasticity at 25.degree. C. of 0.2 to
3.0 GPa, a glass transition temperature of 180.degree. C. or higher
and a 5% weight-loss temperature of 300.degree. C. or higher; a
step of forming a second wiring layer on the resin layer which is
electrically connected to an electrode on the semiconductor wafer;
a step of forming a plural number of protective layers of the
second wiring layer by printing the above resin on the second
wiring layer; a step of providing a through hole (s) at the
protective layer of the second wiring layer penetrating to of the
second wiring layer; and a step of forming an outer electrode
terminal to the through hole (s); and a step of cutting the
semiconductor wafer to obtain respective semiconductor devices.
Next, preferred embodiment of the present invention is explained by
referring to the drawings. FIG. 1 is a sectional view showing
preparation steps of a semiconductor device to explain one example
of the present invention.
FIG. 1(a) is a drawing showing a general structure of a
semiconductor wafer. A semiconductor wafer 3 of the present
invention is not particularly limited so long as it is formed
thereon an electronic circuit or a semiconductor element, and any
kinds or sizes of semiconductor wafers may be used. For example,
there may be mentioned a semiconductor wafer on which a memory
circuit is formed, a semiconductor wafer on which a logic circuit
is formed, etc. On the upper surface of the semiconductor wafer 3,
there is an electrode pad 5, and it may be an electrode pad
constituted by aluminum or produced by gold plating. Moreover, on
the upper surface of the semiconductor wafer 3, an insulating layer
such as a polyimide film 4 is formed. This polyimide film 4 may be
a nitride film such as silicon nitride, aluminum nitride, etc.,
without any specific problem. The position of the polyimide film 4
to be formed is preferably a position covering at least an
electronic circuit on the semiconductor wafer 3, more preferably a
position excluding a dicing area 8 which is finally to cut the
semiconductor wafers to the respective semiconductor devices.
FIG. 1(b) is a drawing in which a resin layer 1 is formed on the
semiconductor wafer 3. A kind of the resin for forming the resin
layer 1 is not specifically limited so long as it is capable of
subjecting to printing, and there may be mentioned, for example, an
epoxy resin, a silicone resin, a phenol resin, a polyimide resin, a
polyamide imide resin, etc.
A modulus of elasticity of the resin for forming the resin layer 1
is required to be 0.2 to 3.0 GPa. If the modulus of elasticity of
the resin exceeds 3.0 GPa, a stress caused by the difference in
thermal expansion coefficients between the semiconductor chip and
the substrate on which the semiconductor device is practically
mounted cannot sufficiently be relaxed by the resin layer 1 so that
crack, etc. occurs at the connecting portion such as solder, etc.
whereby reliability of the semiconductor device cannot be ensured.
Also, if the modulus of elasticity of the resin is less than 0.2
GPa, based on the difference in thermal expansion coefficients
between the semiconductor chip and the substrate on which the
semiconductor device is practically mounted, a second wiring layer
6 formed on the resin layer 1 at the edge portion of the resin
layer 1 likely accepts strain repeatedly so that line breakage
sometimes occurs. Thus, it is preferably 0.2 to 1.0 GPa. Adjustment
of the modulus of elasticity of the resin layer can be accomplished
by formulating a filler, or by using a resin having high elasticity
as a main component of the resin layer like the resin as mentioned
above and formulating a resin having a low modulus of elasticity
therein and changing the formulation ratio thereof.
The resin for insulating the semiconductor of the present invention
is characterized in that the modulus of elasticity at 25.degree. C.
of the resin layer is 0.2 to 3.0 GPa, and the modulus of elasticity
of the above-mentioned resin layer at 150.degree. C. is a size of
10 to 100% to the modulus of elasticity of the same at -65.degree.
C., and preferably a glass transition temperature of the resin
layer is 180.degree. C. or higher. As the resin for forming the
resin layer, there may be mentioned the above-mentioned resin
composition and the heat-resistant resin paste.
The resin having a low modulus of elasticity is preferably rubber
or elastomer such as an acryl, fluorine rubber, butadiene rubber,
silicone, etc., and they are particularly preferably in the shape
of particles.
Here, the modulus of elasticity is a storage modulus of elasticity
and measured by a viscoelastic spectrometer. In the present
invention, it is measured by using a viscoelasticity analyzer RSAII
manufactured by Rheometric Scientific F.E.K.K., with a temperature
raising rate of 5.degree. C./min and a frequency of 1 Hz.
At an edge portion of the resin layer to be formed on the
semiconductor substrate, the maximum value of an angle formed by a
plane surface portion of the semiconductor substrate and a tangent
line of the resin layer surface to the thickness direction of the
edge portion of the resin layer is preferably 45.degree. or less,
particularly preferably 5.degree. or more to 300.degree. or less.
If the maximum value of the above-mentioned angle exceeds
45.degree., formation of a second wiring layer by sputtering,
deposition or plating, etc., on the resin layer becomes
difficult.
A modulus of elasticity of the resin layer 1 at 150.degree. C. is
required to be a size of 10 to 100% to a modulus of elasticity of
the same at -65.degree. C. If it is less than 10%, for example,
when a semiconductor device is subjected to a temperature cycle
from -65 to 150.degree. C. repeatedly, the modulus of elasticity of
the resin layer becomes rapidly large at a low temperature so that
non-elastic strain likely occurs at the connecting portion such as
a solder ball, etc., whereby reliability is lowered. Thus, it is
preferably 50 to 90%.
A glass transition temperature of the resin forming the resin layer
1 is preferably 180.degree. C. or higher. If the glass transition
temperature of the resin layer is less than 180.degree. C., for
example, in a step of forming a second wiring layer 6 on the resin
layer by sputtering, etc., the resin is exposed to a high
temperature so that there is a problem that the resin is thermally
decomposed. The glass transition temperature is more preferably
200.degree. C. or higher.
A 5% weight loss temperature of the resin forming the resin layer 1
is preferably 300.degree. C. or higher. If the 5% weight loss
temperature is less than 300.degree. C., for example, in a step of
forming a second wiring layer 6 by sputtering, etc., the resin is
exposed to a high temperature so that there is a problem that the
resin is thermally decomposed.
Moreover, it is preferred that a drying or curing temperature of
the resin is 250.degree. C. or less since deterioration of the
characteristics of the semiconductor device becomes small.
The resin to be used in the present invention is preferably in the
form of a resin paste which is capable of coating it by printing or
dispense and drying and curing to form a resin layer in the step of
forming a plural number of resin layers since formation of the
resin layer is easy. Also, it is preferred that a viscosity of the
resin paste is 1 to 1000 Pas and a thixotropic coefficient of the
above-mentioned resin paste is 1.2 to 10.0. here, the thixotropic
coefficient (TI value) is shown by a ratio of an apparent viscosity
.eta.1 at a rotation number of 1 min.sup.-1 and .eta.10 at a
rotation number of 10 min.sup.-1, .eta.1/.eta.10.
If the viscosity of the resin paste is less than 1 Pas, it is
easily flown when the resin layer is formed, so that a pattern with
high precision and high density can be hardly obtained. Also, if it
exceeds 1000 Pas, the viscosity is too high and formation of the
insulating layer likely fails.
A formation method of the resin layer is not specifically limited
and can be formed by any methods. For example, there may be
mentioned a method of forming a resin layer on the surface of a
semiconductor substrate by spin coating, a method of forming resin
layers by laminating a resin formed to a film state on the surface
of a semiconductor substrate, etc., and particularly preferably, a
method of forming a resin layer by subjecting the resin paste to
screen printing or metal printing on the surface of a semiconductor
substrate, a method of forming a resin layer by subjecting the
resin paste to dispense on the surface of a semiconductor
substrate, since loss of a material or a number of steps can be
reduced.
The resin layer 1 can be also formed by printing a resin using a
metal mask. At this time, to thicken the resin layer 1, printing
may be repeated with a plural number of times. A thickness of the
resin layer 1 is not particularly limited, and it is preferably
thick in the point of stress relaxation. The thickness is not
particularly limited and preferably 50 to 100 .mu.m. If it is less
than 50 .mu.m, a stress absorbing effect becomes poor. On the other
hand, if it exceeds 100 .mu.m, a stress absorbing effect is further
preferably improved but a thickness of the semiconductor device
becomes thick so that the device cannot be made thin. A position of
printing the resin layer 1 is preferably covering at least an
electronic circuit on the semiconductor wafer 3 completely and
removing at least a dicing area 8.
FIG. 1(c) is a drawing in which holes are formed at desired
position of the resin layer 1. As a method of forming holes to the
resin layer 1, it is carried out by laser to make the state that an
electrode pad 5 is exposed.
FIG. 1(d) is a drawing in which a second wiring layer 6 is formed
on the upper surface of the resin layer 1. A forming method of the
second wiring layer 6 is not particularly limited. It is carried
out, for example, by forming a sputter metal layer such as Cr,
etc., is formed by using a sputter apparatus on the upper surface
of the resin layer 1, coating a plate resist on the sputter metal
film, subjecting to exposing and developing treatments to the
portion at which a Cu plate wiring is to be formed, and after
reaching the Cu wiring to the desired thickness, removing the plate
resist, and further removing the portion at which the sputter metal
film is exposed.
Or else, when the printing portion of the resin layer 1 is made the
range in which it completely covers at least an electronic circuit
and removes at least the electrode pad 5, the second wiring layer 6
can be formed without forming holes by laser, etc. Since at the
edge portion of the resin layer 1 formed by printing, the resin has
fluidity so that it does not completely regenerate the shape of the
opening portion of the metal mask completely and it becomes a
sagged state. When a wiring is formed at this portion, a second
wiring layer 6 which electrically connects the electrode pad 5 and
an outer electrode terminal 7 can be formed without forming holes
by laser. For example, the resin layer 1 is printed at the range
which completely covers an electronic circuit but not covers at
least the electrode pad 5, a sputter metal film such as Cr, etc.,
is formed on the upper surface of the resin layer 1 by using a
sputter apparatus, a plate resist is coated on the upper surface of
the resin layer 1, a Cu wiring is formed by exposure and developing
treatments at the portion at which a Cu plating wiring is desired
to be formed, a Cu wiring is formed by an electroplating at the
portion at which the sputter metal film is exposed, and after the
Cu wiring reaches to a desired thickness, the plate resist is
removed and further the portion at which the sputter metal film is
exposed is removed.
FIG. 1(e) is a drawing in which a protective layer 2 of the second
wiring layer is formed. The position of printing the protective
layer 2 of the second wiring layer is preferably within the range
at which it covers at least the second wiring layer 6 completely
but does not cover at least the dicing area 8. A thickness of the
protective layer 2 of the second wiring layer is not particularly
limited, and preferably, for example, 10 to 50 .mu.m. Also, the
resin which forms the protective layer 2 of the second wiring layer
preferably comprises the same composition as the resin composition
for forming the resin layer 1, and the composition ratio is more
preferably the same. For example, the protective layer 2 of the
second wiring layer and the resin layer 1 comprises the same
composition, but a value of the modulus of elasticity may be
changed by changing an amount of the filler. When the same
compositions are used in the protective layer 2 of the second
wiring layer and the resin layer 1, compatibility of these layers
are good and adhesiveness is also excellent.
FIG. 1(f) is a drawing in which an outer connecting terminal 7 is
formed by opening holes at the desired position(s) of the
protective layer 2 of the second wiring layer. A method of forming
holes of the protective layer 2 of the second wiring layer, it is
carried out by laser to make the state that the second wiring layer
6 is exposed.
FIG. 1(g) is a drawing in which respective semiconductor devices
are formed by cutting the semiconductor wafer 3 is cut at the
dicing area 8. Mounting of solder balls to the outer connecting
terminals may be carried out either before or after dicing the
semiconductor wafer.
EXAMPLES
In the following, the present invention is specifically explained
in detail by referring to Examples and Comparative examples, but
the scope of the present invention is not limited by these.
Example 1
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator was charged 98.4 g (240 mmol) of
2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) under nitrogen
atmosphere, and 700 g of N-methyl-2-pyrrolidone (NMP) was added
thereto to dissolve the mixture. Next, while cooling the mixture
not to exceed 20.degree. C., 51.2 g (244 mmol) of trimellitic
anhydride chloride (TAC) was added to the mixture. After stirring
the mixture at room temperature for one hour, 30.3 g (300 mmol) of
triethylamine was added while cooling the mixture not to exceed
20.degree. C., and the resulting mixture was reacted at room
temperature for 3 hours to produce a polyamic acid varnish. The
resulting polyamic acid varnish was further subjected to
dehydration reaction at 190.degree. C. for 6 hours to produce a
varnish of a polyether amide imide. This varnish of the polyether
amide imide was poured into water and the resulting precipitates
were separated, crushed and dried to obtain a polyether amide imide
powder which is soluble in a polar solvent at room temperature.
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator was charged 98.4 g (240 mmol) of
2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) under nitrogen
atmosphere, and 700 g of N-methyl-2-pyrrolidone (NMP) was added
thereto to dissolve the mixture. Next, while cooling the mixture
not to exceed 20.degree. C., 24.8 g (122 mmol) of isophthalic acid
dichloride (IPC) and 39.4 g (122 mmol) of
3,4,3',4'-benzophenonetetracarboxylic acid dianhydride were added
to the mixture. After stirring the mixture at room temperature for
one hour, 30.3 g (300 mmol) of triethylamine was added while
cooling the mixture not to exceed 20.degree. C., and the resulting
mixture was reacted at room temperature for 3 hours to produce a
polyamic acid varnish. The resulting polyamic acid varnish was
further subjected to dehydration reaction at 190.degree. C. for 6
hours to produce a varnish of a polyether amide imide. This varnish
of the polyether amide imide was poured into water and the
resulting precipitates were separated, crushed and dried to obtain
a polyether amide imide powder which is insoluble in a polar
solvent at room temperature but soluble by heating.
In a 300 ml four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 15 g of the polyether amide imide
powder which is soluble in a polar solvent at room temperature
obtained above, 15 g of the polyether amide imide powder which is
insoluble in a polar solvent at room temperature but soluble by
heating obtained above and 70 g of .gamma.-butyrolactone, and the
mixture was stirred. Next, the mixture was stirred at 150.degree.
C. for one hour. At this time, the varnish which had been ununiform
at room temperature became uniform after heating. After stopping
heating, the mixture was cooled by allowing to stand to the room
temperature while stirring to obtain a yellow-brownish paste
containing two kinds of the resins. A viscosity and a thixotropy
coefficient (TI value) of the resulting paste were measured by
using a CVO rheometer, etc. which is manufactured by Jusco
International Co.
The resulting paste was used for printing by using a screen printer
(New Long Seimitsu Kogyo K.K., Japan, LS-34GX attached with an
alignment device), a meshless metal plate made of nickel alloy
additive plating (manufactured by Mesh Kogyo Co., Japan, thickness:
50 .mu.m, a pattern size: 8 mm.times.8 mm) and Permalex Metal
Squeeze (imported by Tomoe Kogyosha, Co., Japan), and the printing
property was measured. After printing, a pattern was observed by an
optical microscope, and presence or absence of blurring and sag was
observed.
The resulting paste was coated on a Teflon substrate, and heated to
250.degree. C. to evaporate the organic solvent whereby a coated
film having a thickness of 25 .mu.m was formed. This film was
attached to a dynamic viscoelastic spectrometer (manufactured by
K.K. Iwamoto Seisakusho, Japan) and a tensile modulus of elasticity
(25.degree. C., 10 Hz), modulus of elasticities at -65.degree. C.
and 150.degree. C. (frequency: 10 Hz, temperature raising rate:
2.degree. C./min) and a glass transition temperature (frequency: 10
Hz, temperature raising rate: 2.degree. C./min) thereof were
measured. Also, by using a thermobalance, a heat decomposition
starting temperature was measured.
The resulting paste was coated on a semiconductor substrate on
which a wiring had been formed by screen printing to form a plural
number of resin layers, and then, a step of drying, a step of
forming a re-wiring on the resin layer, which is electrically
connected to an electrode on the semiconductor substrate, a step of
forming a protective layer on the re-wiring, and a step of forming
an outer electrode terminal to the protective layer, and subjecting
to dicing to obtain a semiconductor device. This semiconductor
device was subjected to a heat cycle test (-55.degree. C./30
min<-->125.degree. C./30 min, 1000 cycles), and it was
examined whether crack is formed at the resin layer or not. The
semiconductor device is evaluated where no crack was occurred as O,
and crack was occurred as X. The evaluation results of the
above-mentioned resin composition and semiconductor device are
shown in Table 1.
Example 2
Production of the resin composition and the semiconductor device,
and the evaluations thereof were conducted in the same manner as in
Example 1 except that, in a synthesis of a polyether amide imide
which is soluble in a polar solvent at the room temperature, a
diamine compound was changed to 93.3 g (216 mmol) of
bis[4-(4-aminophenoxy)phenyl]phenyl]sulfone (BAPS) and 6.0 g (24
mmol)of 1,3-bis(aminopropyl)tetramethyldisiloxane. The results are
shown in Table 1.
Example 3
Production of the resin composition and the semiconductor device,
and the evaluations thereof were conducted in the same manner as in
Example 1 except that, in a synthesis of a polyether amide imide
which is soluble in a polar solvent at the room temperature, a
diamine compound was changed to 78.7 g (192 mmol) of
2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 6.0 g (24 mmol) of
1,3-bis(aminopropyl)tetramethyldisiloxane and 4.8 g (24 mmol) of
4,4'-diaminodiphenyl ether, an acid compound was changed to 24.8 g
(122 mmol) of isophthalic acid dichloride and 25.6 g (122 mmol) of
trimellitic anhydride chloride. The results are shown in Table
1.
Example 4
Production of the resin composition and the semiconductor device,
and the evaluations thereof were conducted in the same manner as in
Example 1 except that, in a synthesis of a polyether amide imide
which is insoluble in a polar solvent at the room temperature but
soluble by heating, a diamine compound was changed to 93.3 g (216
mmol) of bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS) and 6.0 g (24
mmol) of 1,3-bis(aminopropyl)tetramethyldisiloxane. The results are
shown in Table 1.
Example 5
Production of the resin composition and the semiconductor device,
and the evaluations thereof were conducted in the same manner as in
Example 1 except that, in a synthesis of a polyether amide imide
which is insoluble in a polar solvent at the room temperature but
soluble by heating, a diamine compound was changed to 78.7 g (192
mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 6.0 g (24
mmol) of 1,3-bis(aminopropyl)tetramethyldisiloxane and 4.8 g (24
mmol) of 4,4'-diaminodiphenyl ether, an acid compound was changed
to 12.4 g (61 mmol) of isophthalic acid dichloride, 12.8 g (61
mmol) of trimellitic anhydride chloride and 39.4 g (122 mmol) of
3,4,3',4'-benzophenonetetracarboxilic acid dianhydride. The results
are shown in Table 1.
Example 6
To 100 g of the yellow-brownish paste obtained in Example 1,
containing 2 kinds of resins, that is, polyether amide imide that
is soluble in a polar solvent and polyether amide imide that is
insoluble in a polar solvent but soluble by heating, were added 10
g of silicone rubber filler E-601 (Dow Corning Toray Silicone Co.,
Ltd.), having an average particle size of 2 .mu.m, and the surface
thereof being modified with epoxy groups. The mixture was mixed and
kneaded and dispersed with three-roll mills to obtain a
yellow-brownish paste.
As an evaluation of dispersibility of this paste, it was analyzed
with respect to presence or absence of precipitates after being
left for one week, and presence or absence of coagulation during a
preparation of a coating film.
Using this paste, the evaluations of the resin composition, as well
as production and evaluations of the semiconductor device were
conducted in the same manner as in Example 1. The results are shown
in Table 1.
Example 7
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that an amount of the silicone rubber filler
having an average particle size of 2 .mu.m and the surface thereof
being modified with epoxy groups, was changed to 15 g. The results
are shown in Table 1.
Example 8
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that an amount of the silicone rubber filler
having an average particle size of 2 .mu.m and the surface thereof
being modified with epoxy groups, was changed to 20 g. The results
are shown in Table 1.
Example 9
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that an amount of the silicone rubber filler
having an average particle size of 2 .mu.m and the surface thereof
being modified with epoxy groups, was changed to 25 g. The results
are shown in Table 1.
Example 10
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that an amount of the silicone rubber filler
having an average particle size of 2 .mu.m and the surface thereof
being modified with epoxy groups, was changed to 30 g. The results
are shown in Table 1.
TABLE-US-00001 TABLE 1 Example Item 1 2 3 4 5 6 7 8 9 10 Resin Di-
Formula (I) .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle.- .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. soluble in amine Aromatic diamine other
than -- -- .largecircle. -- -- -- -- -- -- -- polar solvent formula
(I) at room Aliphatic diame -- .largecircle. .largecircle. -- -- --
-- -- -- -- temperature Acid Dicarboxylic acid -- -- .largecircle.
-- -- -- -- -- -- -- Tricarboxylic acid .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle- . .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. Resin Di-
Formula (I) .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle.- .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. insoluble in amine Aromatic diamine
other than -- -- -- -- .largecircle. -- -- -- -- -- polar solvent
formula (I) at room Aliphatic diamine -- -- -- .largecircle.
.largecircle. -- -- -- -- -- temperature Acid Dicarboxylic acid
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle- . .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. but soluble Tricarboxylic acid -- -- --
-- .largecircle. -- -- -- -- -- by heating Tetracarboxylic acid
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle- . .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Amount of resin 100 100 100 100 100 30
30 30 30 30 Amount of low elasticity filler -- -- -- -- -- 10 15 20
25 30 Chemical modification of filler surface -- -- -- -- -- Done
Done Done Done Done Average particle size of filler [.mu.m] -- --
-- -- -- 2.0 2.0 2.0 2.0 2.0 Dispersi- Precipitation -- -- -- -- --
None None None None None bility Aggregated material -- -- -- -- --
None None None None None Viscosity [Pa s] 580 540 560 560 520 540
580 550 530 560 TI Value 4.5 4.0 4.5 3.4 3.8 3.6 4.0 3.8 4.2 4.0
Printing property (presence of blur sag) None None None None None
None None None None None Modulus of elasticity 25.degree. C. 2.8
2.8 2.8 2.8 2.8 2.5 2.0 1.5 1.0 0.5 [GPa] -65.degree. C. 3.2 3.2
3.2 3.2 3.2 2.9 2.4 1.8 1.2 0.6 150.degree. C. 2.5 2.5 2.5 2.5 2.5
2.2 1.8 1.2 0.8 0.3 Elasticity changed ratio at 150.degree.
C./-65.degree. C. [%] 78 78 78 78 78 76 75 67 67 50 Glass
transition temperature (Tg) [.degree. C.] 240 230 230 230 240 220
215 210 205 200 Thermal decomposition initiating temperature
[.degree. C.] 440 430 435 440 430 420 415 410 405 400 Evaluation of
semiconductor device .largecircle. .largecircle. .largecircle.
.largecircle. .largecirc- le. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle.
Example 11
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator was charged 98.4 g (240 mmol) of
2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) as a diamine
compound, under nitrogen atmosphere, and 700 g of
N-methyl-2-pyrrolidone (NMP) was added to dissolve the mixture.
Next, while cooling the mixture not to exceed 20.degree. C., 80.6 g
(260 mmol) of bis(3,4-dicarboxyphenyl)ether dianhydride was added
to the mixture. After being stirred at room temperature for one
hour, the mixture was further subjected to dehydration reaction at
190.degree. C. for 6 hours to produce a varnish of a polyether
amide imide. This varnish of the polyether amide imide was poured
into water and the resulting precipitates were separated, crushed
and dried to obtain a polyether imide powder which is insoluble in
a polar solvent at room temperature but soluble by heating.
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 1, except that polyether imide powder obtained above was
used in place of polyether amide imide powder that is insoluble in
a polar solvent but soluble by heating. The results are shown in
Table 2.
Example 12
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 1, except that in a synthesis of polyether amide imide used
in Example 1, which is soluble in an polar solvent at the room
temperature, a diamine compound was changed to 93.3 g (216 mmol) of
2,2-bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS) and 6.0 g (24 mmol)
of 1,3-bis(aminopropyl)tetramethyldisiloxane, and polyether imide
powder obtained in Example 11 was used in place of polyether amide
imide powder that is insoluble in a polar solvent at the room
temperature but soluble by heating. The results are shown in Table
2.
Example 13
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 1, except that in a synthesis of polyether amide imide in
Example 1, which is soluble in a polar solvent at the room
temperature, a diamine compound was changed to 78.7 g (192 mmol) of
2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 6.0 g (24 mmol) of
1,3-bis(aminopropyl)tetramethyldisiloxane and 4.8 g (24 mmol) of
4,4'-diaminodiphenyl ether, an acid compound was changed to 24.8 g
(122 mmol) of isophthalic acid dichloride and 25.6 g (122 mmol) of
trimellitic anhydride chloride and polyether imide powder obtained
in Example 11 was used in place of polyether amide imide powder
that is insoluble in a polar solvent at the room temperature but
soluble by heating. The results are shown in Table 2.
Example 14
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 1, except that in a synthesis of polyether imide employed
in Example 11, which is insoluble in an polar solvent at the room
temperature but soluble by heating, a diamine compound was changed
to 93.3 g (216 mmol) of bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS)
and 6.0 g (24 mmol) of 1,3-bis(aminopropyl)tetramethyldisiloxane.
The results are shown in Table 2.
Example 15
Production of the resin composition and the semiconductor device,
and the evaluations thereof were conducted in the same manner as in
Example 1 except that, in a synthesis of a polyether imide employed
in Example 11, which is insoluble in a polar solvent at the room
temperature but soluble by heating, a diamine compound was changed
to 78.7 g (192 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane
(BAPP), 6.0 g (24 mmol) of
1,3-bis(aminopropyl)tetramethyldisiloxane and 4.8 g (24 mmol) of
4,4'-diaminodiphenyl ether. The results are shown in Table 2.
Example 16
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that polyether imide obtained in Example 11 was
used in place of polyether amide imide used in Example 6, which is
insoluble in a polar solvent at the room temperature but soluble by
heating. The results are shown in Table 2.
Example 17
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that polyether imide obtained in Example 11 was
used in place of polyether amide imide used in Example 6, which is
insoluble in a polar solvent at the room temperature but soluble by
heating, and an amount of the silicone rubber filler having an
average particle size of 2 .mu.m and the surface thereof being
modified with epoxy groups, was changed to 15 g. The results are
shown in Table 2.
Example 18
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that polyether imide obtained in Example 11 was
used in place of polyether amide imide used in Example 6, which is
insoluble in a polar solvent at the room temperature but soluble by
heating, and an amount of the silicone rubber filler having an
average particle size of 2 .mu.m and the surface thereof being
modified with epoxy groups, was changed to 20 g. The results are
shown in Table 2.
Example 19
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that polyether imide obtained in Example 11 was
used in place of polyether amide imide used in Example 6, which is
insoluble in a polar solvent at the room temperature but soluble by
heating, and an amount of the silicone rubber filler having an
average particle size of 2 .mu.m and the surface thereof being
modified with epoxy groups, was changed to 25 g. The results are
shown in Table 2.
Example 20
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example 6, except that polyether imide obtained in Example 11 was
used in place of polyether amide imide used in Example 6, which is
insoluble in a polar solvent at the room temperature but soluble by
heating, and an amount of the silicone rubber filler having an
average particle size of 2 .mu.m and the surface thereof being
modified with epoxy groups, was changed to 30 g. The results are
shown in Table 2.
Comparative Example 1
Production of the resin composition and the semiconductor device
and the evaluations thereof were conducted in the same manner as in
Example l, except that a resin composition consisting only of
polyether amide imide that is soluble in a polar solvent at the
room temperature was used in place of polyether amide imide that is
insoluble in a polar solvent at the room temperature but soluble by
heating. As a result, TI value of the resin composition was 1.0,
and in the valuation of printing property, blurring and sag were
observed.
In addition, it was impossible to produce a semiconductor device
using this composition. The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Comparative Example example Item 11 12 13 14
15 16 17 18 19 20 1 Resin soluble in Di- Formula (I) .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.-
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .la- rgecircle. polar solvent at amine Aromatic
diamine other -- -- .largecircle. -- -- -- -- -- -- -- -- room
temperature than formula (I) Aliphatic diame -- .largecircle.
.largecircle. -- -- -- -- -- -- -- -- Acid Dicarboxylic acid -- --
.largecircle. -- -- -- -- -- -- -- -- Tricarboxylic acid
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle- . .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .l- argecircle. Resin insoluble Di-
Formula (I) .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle.- .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .la- rgecircle. in polar solvent amine
Aromatic diamine other -- -- -- -- .largecircle. -- -- -- -- -- --
at room tem- than formula (I) perature but Aliphatic diamine -- --
-- .largecircle. .largecircle. -- -- -- -- -- -- soluble by Acid
Tetracarboxylic acid .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle- . .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. --- heating Amount of
resin 100 100 100 100 100 30 30 30 30 30 100 Amount of low
elasticity filler -- -- -- -- -- 10 15 20 25 30 -- Chemical
modification of filler surface -- -- -- -- -- Done Done Done Done
Done -- Average particle size of filler [.mu.m] -- -- -- -- -- 2.0
2.0 2.0 2.0 2.0 -- Dispersi- Precipitation -- -- -- -- -- None None
None None None -- bility Aggregated material -- -- -- -- -- None
None None None None -- Viscosity [Pa s] 570 540 550 570 530 550 570
560 530 570 550 TI Value 4.3 4.1 4.4 3.5 3.9 3.8 4.2 3.9 4.1 4.2
1.0 Printing property (presence of blur sag) None None None None
None None None None None None Present Modulus of elasticity
25.degree. C. 2.9 2.9 2.9 2.9 2.9 2.5 2.0 1.5 1.0 2.8 2.8 [GPa]
-65.degree. C. 3.2 3.2 3.2 3.2 3.2 2.9 2.4 1.8 1.2 3.2 3.2
150.degree. C. 2.5 2.5 2.5 2.5 2.5 2.2 1.8 1.2 0.8 2.5 2.5
Elasticity changed ratio at 150.degree. C./-65.degree. C. [%] 78 78
78 78 78 76 75 67 67 50 78 Glass transition temperature (Tg)
[.degree. C.] 240 230 235 230 240 225 215 210 205 200 240 Thermal
decomposition initiating temperature [.degree. C.] 450 440 440 430
440 420 415 410 405 400 440 Evaluation of semiconductor device
.largecircle. .largecircle. .largecircle. .largecircle. .largecirc-
le. .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. - Impossi- ble to prepare
Synthesis Example 1 (Heat-resistant Resin A''-1)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 96.7 g (0.3 mol) of
3,4,3'4'-benzophenonetetracarboxylic acid dianhydride (hereinafter
referred to as BTDA), 36.0 g (0.18 mol) of 4,4'-diaminodiphenyl
ether (hereinafter referred to as DDE), 43.1 g (0.105 mol) of
2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter referred to
as BAPP), 3.73 g (0.015 mol) of
1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 381.5 g of
.gamma.-butyrolactone under nitrogen atmosphere.
The resultant mixture was subjected to a reaction at a temperature
of 60 to 65.degree. C. for 2 hours under stirring. The reaction was
terminated by cooling the mixture at a point where a number average
molecular weight reached 50,000 (polystyrene converted value). The
thus obtained solution was diluted by .gamma.-butyrolactone to
obtain a polyimide precursor (heat-resistant resin A''-1) solution
having a resin concentration of 30% by weight.
Synthesis Example 2 (Heat-resistant Resin B''-1)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 109.6 g (0.4 mol) of BTDA, 76.1 g
(0.38 mol) of DDE, 4.97 g (0.02 mol) of
1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 405.2 g of
.gamma.-butyrolactone under nitrogen atmosphere.
The resultant mixture was subjected to a reaction at a temperature
of from 60.degree. C. to 65.degree. C. for 2 hours under stirring.
The reaction was terminated by cooling the mixture at a point where
a number average molecular weight reached 35,000 (polystyrene
converted value). The thus obtained solution was diluted by
.gamma.-butyrolactone to obtain a polyimide precursor solution
(heat-resistant resin B''-1) having a resin concentration of 30% by
weight.
Preparation Example 1 (Heat-resistant Resin Based Paste: Heat
Resistant Resin A''-1/Heat-resistant Resin B''-1)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 150 g of the above described
heat-resistant resin B-1 polyimide precursor solution (resin
concentration of 30% by weight) and 350 g of the above described
heat-resistant resin A-1 polyimide precursor solution (resin
concentration of 30% by weight), under nitrogen atmosphere. The
resultant mixture was subjected to stirring at a temperature of 60
to 65.degree. C. for one hour to obtain a uniform transparent
solution. The mixture was further subjected to stirring at a
temperature of 60 to 65.degree. C. for 24 hours, whereby
heat-resistant resin B''-1 polyimide precursor particles are
precipitated and dispersed in the solution. This was diluted by
.gamma.-butyrolactone to obtain a polyimide type heat-resistant
resin past (1) having a viscosity of 480 Pas and thixotropic
coefficient (hereinafter referred as to TI value) of 3.0. The
heat-resistant resin B''-1 polyimide precursor particles in the
polyimide type heat-resistant resin paste (1) were insoluble in
.gamma.-butyrolactone at the room temperature but soluble at
80.degree. C.
The above described polyimide type heat-resistant resin paste (1)
was coated on a glass substrate (thickness; about 2 mm), by a bar
coater coating whereby a coated film having a thickness of 50 .mu.m
after heat drying was formed. It was subjected to heat-treating at
80.degree. C. for 5 minutes, 100.degree. C. for 10 minutes,
150.degree. C. for 10 minutes, 200.degree. C. for 15 minutes, and
further, 300.degree. C. for 60 minutes, to obtain a glass substrate
coated with polyimide type resin composition (1). The coated film
was almost uniform and transparent, and the heat-resistant resin
B''-1 polyimide precursor particles in the polyimide type
heat-resistant resin paste (1) were dissolved in
.gamma.-butyrolactone while a heating process, they were further
dehydrated and cyclized together with a heat-resistant resin A''-1
polyimide precursor, being dissolved in a state of polyimide resin
in the solution.
Synthesis Example 3 (Heat-resistant Resin A''-2)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 77.3 g (0.24 mol) of BTDA, 31.4 g
(0.06 mol) of 1,10-(decamethylene)bis(trimellitate dianhydride),
36.0 g (0.18 mol) of DDE, 43.1 g (0.105 mol) of BAPP, 3.73 g (0.015
mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 381.5 g of
.gamma.-butyrolactone under nitrogen atmosphere.
The resultant mixture was subjected to a reaction at a temperature
of 60 to 65.degree. C. for 2 hours under stirring. The reaction was
terminated by cooling the mixture at a point where a number average
molecular weight reached 60,000 (polystyrene converted value). The
thus obtained solution was diluted by .gamma.-butyrolactone to
obtain a polyimide precursor solution (heat-resistant resin A''-2)
having a resin concentration of 30% by weight.
Preparation Example 2 (Heat-resistant Resin Based Paste: Heat
Resistant Resin A''-2/Heat-resistant Resin B''-1)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 100 g of the above described
heat-resistant resin B''-1 polyimide precursor solution (resin
concentration of 30% by weight) and 400 g of the above described
heat-resistant resin A''-2 polyimide precursor solution (resin
concentration of 30% by weight), under nitrogen atmosphere. The
resultant mixture was subjected to stirring at a temperature of 60
to 65.degree. C. for one hour to obtain a uniform transparent
solution. The mixture was further subjected to stirring at a
temperature of 60 to 65.degree. C. for 34 hours, whereby
heat-resistant resin B''-1 polyimide precursor particles are
precipitated and dispersed in the solution. This was diluted by
.gamma.-butyrolactone to obtain a polyimide type heat-resistant
resin past (2) having a viscosity of 450 Pas and thixotropic
coefficient (hereinafter referred as to TI value) of 5.5. The
heat-resistant resin B''-1 polyimide precursor particles in the
polyimide type heat-resistant resin paste (2) were insoluble in
.gamma.-butyrolactone at the room temperature but soluble at
80.degree. C.
The above described polyimide type heat-resistant resin paste (2)
was coated on a glass substrate (thickness; about 2 mm), by a bar
coater coating whereby a coated film having a thickness of 50 .mu.m
after heat drying was formed. It was subjected to heat-treating at
80.degree. C. for 5 minutes, 100.degree. C. for 10 minutes,
150.degree. C. for 10 minutes, 200.degree. C. for 15 minutes, and
further, 250.degree. C. for 60 minutes, to obtain a glass substrate
coated with polyimide type resin composition (2). The coated film
was almost uniform and transparent, and the heat-resistant resin
B''-1 polyimide precursor particles in the polyimide type
heat-resistant resin paste were dissolved in .gamma.-butyrolactone
while a heating process, they were further dehydrated and cyclized
together with a heat-resistant resin A''-2 polyimide precursor,
being dissolved in a state of a polyimide resin in the
solution.
Synthesis Example 4 (Heat-resistant Resin A''-3)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 32.2 g (0.1 mol) of BTDA, 52.2 g
(0.1 mol) of 1,10-(decamethylene)bis(trimellitate dianhydride),
36.0 g (0.18 mol) of DDE, 43.1 g (0.105 mol) of BAPP, 3.73 g (0.015
mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 381.5 g of
.gamma.-butyrolactone under nitrogen atmosphere.
The resultant mixture was subjected to a reaction at a temperature
of 60 to 65.degree. C. for 2 hours under stirring. The reaction was
terminated by cooling the mixture at a point where a number average
molecular weight reached 45,000 (polystyrene converted value). The
thus obtained solution was diluted by .gamma.-butyrolactone to
obtain a polyimide precursor solution (heat-resistant resin A''-3)
having a resin concentration of 30% by weight.
Preparation Example 3 (Heat-resistant Resin Based Paste: Heat
Resistant Resin A''-3/Heat-resistant Resin B''-1)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 250 g of the above described
heat-resistant resin B-1 polyimide precursor solution (resin
concentration of 30% by weight) and 250 g of the above described
heat-resistant resin A-3 polyimide precursor solution (resin
concentration of 30% by weight), under nitrogen atmosphere. The
resultant mixture was subjected to stirring at a temperature of 60
to 65.degree. C. for one hour to obtain a uniform transparent
solution. The mixture was further subjected to stirring at a
temperature of 60 to 65.degree. C. for 14 hours, whereby
heat-resistant resin B''-1 polyimide precursor particles are
precipitated and dispersed in the solution. This was diluted by
.gamma.-butyrolactone to obtain a polyimide type heat-resistant
resin past (3) having a viscosity of 400 Pas and thixotropic
coefficient (hereinafter referred as to TI value) of 4.5. The
heat-resistant resin B''-1 polyimide precursor particles in the
polyimide type heat-resistant resin paste (3) were insoluble in
.gamma.-butyrolactone at the room temperature but soluble at
80.degree. C.
The above described polyimide type heat-resistant resin paste (3)
was coated on a glass substrate (thickness; about 2 mm), by a bar
coater coating whereby a coated film having a thickness of 50 .mu.m
after heat drying was formed. It was subjected to heat-treating at
80.degree. C. for 5 minutes, 100.degree. C. for 10 minutes,
150.degree. C. for 10 minutes, 200.degree. C. for 15 minutes, and
further, 250.degree. C. for 60 minutes, to obtain a glass substrate
coated with polyimide type resin composition (3). The coated film
was almost uniform and transparent, and the heat-resistant resin
B''-1 polyimide precursor particles in the polyimide type
heat-resistant resin paste were dissolved in .gamma.-butyrolactone
while a heating process, they were further dehydrated and cyclized
together with a heat-resistant resin A''-3 polyimide precursor,
being dissolved in a state of polyimide resin in the solution.
Synthesis Example 5 (Heat-resistant Resin A''-4)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 65.69 g (0.16 mol) of BAPP, 143.22
g (0.40 mol) of bis(3,4-dicarboxyphenyl)sulfone dianhydride
(hereinafter referred to as DSDA), 38.84 g (0.20 mol) of
isophthalic acid dihydrazide, 9.93 g (0.04 mol) of
1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 478 g of
.gamma.-butyrolactone under nitrogen atmosphere.
The resultant mixture was subjected to a reaction under stirring at
a temperature of 50 to 60.degree. C. for one hour, then the
temperature was elevated to 195.degree. C. for the reaction to
proceed. The reaction was terminated by cooling the mixture at a
point where a number average molecular weight reached 27,000
(polystyrene converted value). During the reaction, distillated
water was immediately removed out of the reaction system. The thus
obtained solution was diluted by .gamma.-butyrolactone to obtain a
polyamide imide resin solution (heat-resistant resin A''-4) having
a resin concentration of 30% by weight.
Synthesis Example 6 (Heat-resistant Resin B''-2)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 102.6 g (0.25 mol) of BAPP, 77.55
g (0.25 mol) of bis(3,4-dicarboxyphenyl)ether dianhydride
(hereinafter referred to as ODPA), and 335 g of
.gamma.-butyrolactone under nitrogen atmosphere.
The resultant mixture was subjected to a reaction under stirring at
a temperature of 50 to 60.degree. C. for one hour, then the
temperature was elevated to 195.degree. C. for the reaction to
proceed. The reaction was terminated by cooling the mixture at a
point where a number average molecular weight reached 28,000
(polystyrene converted value). During the reaction, distillated
water was immediately removed out of the reaction system. The thus
obtained solution was diluted by .gamma.-butyrolactone to obtain a
polyimide resin solution (heat-resistant resin B''-2) having a
resin concentration of 30% by weight.
Preparation Example 4 (Heat-resistant Resin Based Paste: Heat
Resistant Resin A''-4/Heat-resistant Resin B''-2)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 200 g of the above described
heat-resistant resin B''-2 polyimide resin solution (resin
concentration of 30% by weight) and 466.67 g of the above described
heat-resistant resin A''-4 polyamide imide resin solution (resin
concentration of 30% by weight), under nitrogen atmosphere. The
resultant mixture was subjected to stirring at a temperature of
180.degree. C. for one hour to obtain a uniform transparent
solution. The mixture was cooled down to 23.degree. C. in one hour,
then allowed to stand for 1 month, whereby heat resistant polyimide
resin particles are precipitated and dispersed in the solution.
This was diluted by .gamma.-butyrolactone to obtain a polyimide
type heat-resistant resin past (4) having a viscosity of 380 Pas
and thixotropic coefficient (hereinafter referred as to TI value)
of 2.5. The obtained polyimide resin particle had a maximum
particle diameter of 5 .mu.m or less, being insoluble in
.gamma.-butyrolactone at the room temperature but soluble at
150.degree. C.
The above described polyimide type heat-resistant resin paste (4)
was coated on a glass substrate (thickness; about 2 mm), by a bar
coater coating whereby a coated film having a thickness of 50 .mu.m
after heat drying was formed. It was subjected to heat-treating at
140.degree. C. for 15 minutes, 200.degree. C. for 15 minutes and
further, 300.degree. C. for 60 minutes, to obtain a glass substrate
coated with polyimide type resin composition (4). The coated film
was almost uniform and transparent, and the polyimide resin
particles (heat-resistant resin B''-2) in the polyimide type
heat-resistant resin paste (4) were dissolved in
.gamma.-butyrolactone while a heating process, they were further
observed to be dissolved together with the polyamide imide resin
(heat-resistant resin A''-4) in the solution.
Synthesis Example 7 (Heat-resistant Resin A''-5 )
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator were charged 89.09 g (0.217 mol) of BAPP,
119.59 g (0.334 mol) of DSDA, 42.85 g (0.117 mol) of
2,2-bis(4-hydroxy-3-aminophenyl)hexafluoropropane (hereinafter
referred to as HAB-6F), and 377 g of .gamma.-butyrolactone under
nitrogen atmosphere.
The resultant mixture was subjected to a reaction under stirring at
a temperature of 50 to 60.degree. C. for one hour, then the
temperature was elevated to 195.degree. C. for the reaction to
proceed. The reaction was terminated by cooling the mixture at a
point where a number average molecular weight reached 26,000
(polystyrene converted value). During the reaction, distillated
water was immediately removed out of the reaction system. The thus
obtained solution was diluted by .gamma.-butyrolactone to obtain a
polyimide resin solution (heat-resistant resin A''-5) having a
resin concentration of 40% by weight.
Preparation Example 5 (Heat-resistant Resin Based Paste: Heat
Resistant Resin A''-5/Heat-resistant Resin B''-2)
In a one-liter four-necked flask equipped with a thermometer, a
stirrer, a nitrogen inlet tube, and a condenser equipped with an
oil-water separator was charged 400 g of the above described
heat-resistant resin B''-2 polyimide resin solution (resin
concentration of 30% by weight), under nitrogen atmosphere. The
temperature of the resin was elevated to 180.degree. C. The resin
was subjected to stirring at the same temperature for one hour,
then mixed with 300 g of the above described heat-resistant resin
A''-5 polyimide resin solution (resin concentration of 40%). The
resultant mixture was subjected to stirring at 180.degree. C. for
one hour. The mixture was cooled down to 60.degree. C. in one hour,
then stirred for one day, thereby to obtain a paste in which heat
resistant polyimide resin particles are precipitated and dispersed.
To this paste, 48 g of .gamma.-glycidoxypropyltrimethoxysilane was
added, followed by mixing thoroughly at the room temperature. This
was diluted by .gamma.-butyrolactone to obtain a polyimide type
heat-resistant resin past (5) having a viscosity of 150 Pas and TI
value of 3.5.
The above described polyimide type heat-resistant resin paste (5)
was coated on a glass substrate (thickness; about 2 mm), by a bar
coater coating whereby a coated film having a thickness of 50 .mu.m
after heat drying was formed. It was subjected to heat-treating at
140.degree. C. for 15 minutes, 200.degree. C. for 15 minutes and
further, 300.degree. C. for 60 minutes, to obtain a glass substrate
coated with polyimide type resin composition (5). The coated film
was almost uniform and transparent, and the polyimide resin
particles (heat-resistant resin B''-2) in the polyimide type
heat-resistant resin paste (4) were dissolved in-butyrolactone
while a heating process, they were further observed to be dissolved
together with the polyamide imide resin (heat-resistant resin
A''-5) in the solution.
Example 21
To 200 parts by weight of the polyimide type heat-resistant resin
paste (1) (resin concentration of 30% by weight) obtained in
Preparation Example 1 were added 40 parts by weight of elastic
silicone rubber particles E-601 (Dow Corning Toray Silicone Co.,
Ltd., trade name: TREFIL), having an average particle size of 2
.mu.m, and the surface thereof being modified with epoxy groups and
70 parts by weight of .gamma.-butyrolactone. The mixture was mixed
and kneaded with three-roll mills to prepare a heat-resistant resin
paste (6).
After the resulting heat-resistant resin paste (6) was degassed, it
was coated on a 5 inch silicon wafer by a bar coater coating
whereby a coated film having a thickness of 50 .mu.m after heat
drying was formed. It was subjected to heat-treating at 80.degree.
C. for 5 minutes, 100.degree. C. for 10 minutes, 150.degree. C. for
10 minutes, 200.degree. C. for 15 minutes, and further, 300.degree.
C. for 60 minutes, to obtain a silicon wafer coated with polyimide
type resin composition (6). With respect to the obtained polyimide
type resin composition (6), elasticities, mechanical strength of
the film, and glass transition temperatures were measured
Here, a modulus of elasticity was measured by using a
viscoelasticity analyzer RSAII manufactured by Rheomethoric
Scientific F. E. Co. in air, with a temperature rising rate of
5.degree. C./min and a frequency of 1 Hz. The mechanical strength
of the film was measured by using a Tensilon multi tester UCT-5T
manufactured by Orientech, Co. The glass transition temperature was
measured by using a Thermomechanical analyzer TMA/SS6100
manufactured by Seiko Instruments Co.
Also, by using the heat-resistant resin paste (6), a resin film
pattern was prepared by coating on a 8 inch silicon wafer so that a
thickness after heating and drying becomes 50 .mu.m, using a screen
printer (New Long Seimitsu Kogyo K.K., Japan, LS-34GX attached with
an alignment device), a meshless metal plate made of nickel alloy
additive plating (manufactured by Mesh Kogyo Co., Japan, thickness:
100 .mu.m, a pattern size: 8 mm.times.8 mm) and Permalex Metal
Squeeze (imported by Tomoe Kogyo Co., Japan), and the printing
property thereof was measured. After printing, a pattern was
observed by an optical microscope, and presence or absence of
pattern losing and scratching were observed.
The heat-resistant resin paste (6) obtained above was coated on a
semiconductor substrate on which a wiring had been formed by screen
printing to form a plural number of resin layers, and then, a step
of drying, a step of forming a re-wiring on the resin layer, which
is electrically connected to an electrode on the semiconductor
substrate, a step of forming a protective layer on the re-wiring, a
step of forming an outer electrode terminal to the protective
layer, a step of forming a protective layer excluding a loading
part of solder balls, and a step of loading solder balls were
conducted, followed by dicing to obtain a semiconductor device.
This semiconductor device was subjected to a heat cycle test of
-65.degree. C./15 min and 150.degree. C./15 min for 1000 cycles.
The semiconductor device is evaluated where no abnormality occurred
as good.
The evaluation results of the above-mentioned heat-resistant resin
paste (6), the resin film and the semiconductor device obtained
therefrom are shown in Table 3.
Example 22
To 233 parts by weight of polyimide type heat-resistant resin paste
(2) (resin concentration of 30% by weight) obtained in Preparation
example 2 were added 30 parts by weight of fine particles of
silicone rubber elastic material (TREFIL E-601 available from Dow
Corning Toray Silicone Co., Ltd.) having an average particle size
of 2 .mu.m and the surface thereof being introduced with epoxy
groups and 50 parts by weight of .gamma.-butyrolactone, a
heat-resistant resin paste (7) was prepared by mixing and kneading
with three-roll mills, and the material was evaluated in the same
manner as in Example 21 except for changing the final temperature
of heating to 250.degree. C. The evaluation results of the
above-mentioned heat-resistant resin paste (7), the resin film and
the semiconductor device obtained therefrom are shown in Table
3.
Example 23
To 266 parts by weight of polyimide type heat-resistant resin paste
(3) (resin concentration of 30% by weight) obtained in Preparation
example 3 were added 20 parts by weight of fine particles of
silicone rubber elastic material (TREFIL E-601 available from Dow
Corning Toray Silicone Co., Ltd.) having an average particle size
of 2 .mu.m and the surface thereof being introduced with epoxy
groups and 26 parts by weight of .gamma.-butyrolactone, a
heat-resistant resin paste (8) was prepared by mixing and kneading
with three-roll mills, and the material was evaluated in the same
manner as in Example 22 except for using the paste. The evaluation
results of the above-mentioned heat-resistant resin paste (8), the
resin film and the semiconductor device obtained therefrom are
shown in Table 3.
Example 24
To 200 parts by weight of polyimide type heat-resistant resin paste
(4) (resin concentration of 30% by weight) obtained in Preparation
example 4 were added 40 parts by weight of fine particles of
silicone rubber elastic material (TREFIL E-601 available from Dow
Corning Toray Silicone Co., Ltd.) having an average particle size
of 2 .mu.m and the surface thereof being introduced with epoxy
groups and 70 parts by weight of .gamma.-butyrolactone, a
heat-resistant resin paste (9) was prepared by mixing and kneading
with three-roll mills, and the material was evaluated in the same
manner as in Example 21 except for using the paste. The evaluation
results of the above-mentioned heat-resistant resin paste (9), the
resin film and the semiconductor device obtained therefrom are
shown in Table 3.
Example 25
To 176 parts by weight of polyimide type heat-resistant resin paste
(5) (resin concentration of 30% by weight) obtained in Preparation
example 5 were added 40 parts by weight of fine particles of
silicone rubber elastic material (TREFIL E-601 available from Dow
Corning Toray Silicone Co., Ltd.) having an average particle size
of 2 .mu.m and the surface thereof being introduced with epoxy
groups and 95 parts by weight of .gamma.-butyrolactone, a
heat-resistant resin paste (10) was prepared by mixing and kneading
with three-roll mills, and the material was evaluated in the same
manner as in Example 21 except for using the paste. The evaluation
results of the above-mentioned heat-resistant resin paste (10), the
resin film and the semiconductor device obtained therefrom are
shown in Table 3.
Example 26
To 316 parts by weight of polyimide type heat-resistant resin paste
(2) (resin concentration of 30% by weight) obtained in Preparation
example 2 was added 5 parts by weight of fine particles of silicone
rubber elastic material (TREFIL E-601 available from Dow Corning
Toray Silicone Co., Ltd.) having an average particle size of 2
.mu.m and the surface thereof being introduced with epoxy groups, a
heat-resistant resin paste (11) was prepared by mixing and kneading
with three-roll mills, and the material was evaluated in the same
manner as in Example 22 except for using the paste. The evaluation
results of the above-mentioned heat-resistant resin paste (11), the
resin film and the semiconductor device obtained therefrom are
shown in Table 3.
TABLE-US-00003 TABLE 3 Item Example 21 Example 22 Example 23
Example 24 Example 25 Example 26 Heat-resistant resin A'' A''-1
A''-2 A''-3 A''-4 A''-5 A''-2 Heat-resistant resin B'' B''-1 B''-1
B''-1 B''-2 B''-2 B''-1 Total amount of 60 70 80 60 60 95
heat-resistant resin (solid component) Amount of Rubber elastic 40
30 20 40 40 5 material (silicone rubber filler) Heat-resistant
resin paste (6) (7) (8) (9) (10) (11) Viscosity (Pa s) 350 250 350
200 100 560 TI value 4.2 6.0 5.0 2.4 3.2 6.2 Modulus of elasticity
1.0 1.3 1.4 1.0 1.0 2.7 (GPa) @ -65.degree. C. Modulus of
elasticity 0.8 1.0 1.1 0.8 0.8 2.3 (GPa) @ 25.degree. C. Modulus of
elasticity 0.6 0.7 0.8 0.6 0.6 1.9 (GPa) @ 150.degree. C. Change in
modulus of 60 54 57 60 60 70 elasticity (%) (150.degree.
C./-65.degree. C.) Glass transition 280 220 200 265 255 225
temperature (.degree. C.) 5% Weight loss 420 405 400 375 390 410
temperature (.degree. C.) Mechanical strength (MPa) 40 50 50 30 35
50 Printing Pattern flow None None None None None property Blur
None None None None None Sputter resistance Good Good Good Good
Good Good Temperature cycle test Good Good Good Good Good Good
Comparative Example 2
Evaluations were carried out in the same manner as in Example 21,
except that the polyimide type heat-resistant resin paste (1)
obtained in Preparation Example 1 was used in place of the
heat-resistant resin paste (6) employed in Example 21. As a result,
failure occurred in a heat cycle test of the semiconductor device.
Also, the evaluation results of the above-mentioned polyimide type
heat-resistant resin paste (1), the resin film and the
semiconductor device obtained therefrom are shown in Table 4.
Comparative Example 3
Evaluations were carried out in the same manner as in Example 22,
except that the polyimide type heat-resistant resin paste (2)
obtained in Preparation Example 2 was used in place of the
heat-resistant resin paste (7) employed in Example 22. As a result,
failure occurred in a heat cycle test of the semiconductor device.
Also, the evaluation results of the above-mentioned polyimide type
heat-resistant resin paste (2), the resin film and the
semiconductor device obtained therefrom are shown in Table 4.
Comparative Example 4
Evaluations were carried out in the same manner as in Example 21,
except that the polyimide type heat-resistant resin paste (5)
obtained in Preparation Example 5 was used in place of the
heat-resistant resin paste (6) employed in Example 21. As a result,
failure occurred in a heat cycle test of the semiconductor device.
Also, the evaluation results of the above-mentioned polyimide type
heat-resistant resin paste (5), the resin film and the
semiconductor device obtained therefrom are shown in Table 4.
Comparative Example 5
Evaluations were carried out in the same manner as in Example 22,
except that heat-resistant resin A''-2 solution obtained in
Synthesis Example 3 was used in place of the heat-resistant resin
paste (6) employed in Example 21. As a result, a pattern loosing
occurred at the time of screen printing and the semiconductor
device could not be produced. Also, the evaluation results of the
above-mentioned heat-resistant resin A''-2 solution and the resin
film obtained therefrom are shown in Table 4.
Comparative Example 6
Evaluations were carried out in the same manner as in Example 23,
except that a resin paste, obtained by mixing the heat-resistant
resin A''-3 solution obtained in Synthesis Example 4 and aerosil,
which has a viscosity of 350 Pas and TI value of 5.0 was used in
place of the heat-resistant resin paste (8) employed in Example 23.
As a result, elasticity was 2.8 GPa at -65.degree. C. and 0.2 GPa
at 150.degree. C., and a changed amount of the modulus of
elasticity was 7%. In addition, a glass transition temperature was
reduced to as low as 160.degree. C., and cracking on the surface of
the resin film was observed in a sputtering process during
production of the semiconductor device. As a result, it was
impossible to produce a semiconductor device. The evaluation
results of the above-mentioned resin paste and the resin film
obtained therefrom are shown in Table 4.
TABLE-US-00004 TABLE 4 Comparative Comparative Comparative
Comparative Comparative Item example 2 example 3 example 4 example
5 example 6 Heat-resistant resin A'' A''-1 A''-2 A''-5 A''-2 A''-3
Heat-resistant resin B'' B''-1 B''-1 B''-2 -- -- Total amount of
100 100 100 100 100 heat-resistant resin (solid component) Amount
of Rubber elastic 0 0 0 0 0 material (silicone rubber filler)
Heat-resistant resin paste (1) (2) (5) (A-2 (A-3 solution +
solution) Aerosil) Viscosity (Pa s) 480 450 150 60 350 TI value 3.0
5.5 3.5 1.1 5.0 Modulus of elasticity 3.4 3.3 3.4 3.0 2.8 (GPa) @
-65.degree. C. Modulus of elasticity 3.1 3.1 3.1 2.7 2.3 (GPa) @
25.degree. C. Modulus of elasticity 2.5 2.4 2.4 1.9 0.2 (GPa) @
150.degree. C. Change in modulus of 74 73 71 63 7 elasticity (%)
(150.degree. C./-65.degree. C.) Glass transition temperature 285
225 260 205 160 (.degree. C.) 5% Weight loss 425 410 395 390 380
temperature (.degree. C.) Mechanical strength (MPa) 125 105 110 100
70 Printing Pattern flow None None None Present Present property
Blur None None None -- -- Sputter resistance Good Good Good --
Crack occurred Temperature cycle test Failure Failure Failure -- --
occurred occurred occurred
Example 27
To 233 parts by weight of the polyimide type heat-resistant resin
paste (GH-P500 available from Hitachi Chemical Co., Ltd.) were
added 30 parts by weight of elastic silicone rubber particles
(TREFIL E-601 available from Dow Corning Toray Silicone Co., Ltd.)
having an average particle size of 2 .mu.m and the surface thereof
being modified with epoxy groups and 70 parts by weight of
.gamma.-butyrolactone, and the mixture was mixed and kneaded with
three-roll mills to prepare a heat-resistant resin paste. After the
resulting heat-resistant resin paste was degassed, on a
semiconductor substrate which is a silicon wafer with a diameter of
8 inch and a thickness of 600 .mu.m, on one side of which an
electronic circuit was formed, having the plural number of
electrodes connected to the circuit on the same side, and connected
to the outside on a peripheral part, and on which a polyimide layer
for purpose of protecting the electronic circuit was formed at
least on the surface of the circuit, excluding the electrodes
portion, the resulting heat-resistant resin paste was printed in a
plural number in a state of an island, using a metal mask, at least
on the surface of the circuit, excluding the above mentioned
electrodes. This was heated for hardening purpose at 250.degree. C.
for one hour to obtain a resin layer. Then, on the resin layer
surface of the above mentioned semiconductor substrate, a sputter
layer such as Cr--Cu and Cr--Pd--Cu, etc. is to be formed with a
thickness of 0.1 to 2 .mu.m. Here, by using Cr--Cu, a metal sputter
film with 0.5 .mu.m was formed. Then, to form a second wiring
layer, a plating resist with a thickness of 10 to 40 .mu.m was
formed on the above-mentioned sputter metal layer. A thickness of
the plating resist can be selected according to the desired
thickness of the electrolytic Cu plating. Here, a resist with a
thickness of 20 .mu.m was formed. After exposure, the plating
resist was developed, and electrolytic Cu plating was laminated on
the exposed portion of the sputter metal layer. After plating, the
remaining plating resist was exfoliated to form a second wiring
layer. A protective layer was then formed on the second wiring
layer excluding a mounting part of solder balls. On the
electrolytic Cu plating at which the solder ball (400 .mu.m in
diameter) is to be mounted, 0.3 .mu.m of Ni--Au plating layer was
formed, then the solder balls are mounted. Further, the
above-mentioned semiconductor substrate was cut into pieces using a
silicon wafer dicing device to obtain a semiconductor device.
Here, a modulus of elasticity was measured by using a
viscoelasticity analyzer RSAII manufactured by Rheomethoric
Scientific F. E. Co. with a temperature rising rate of 5.degree.
C./min and a frequency of 1 Hz. A glass transition temperature was
measured by using a Thermomechanical analyzer TMA/SS6100
manufactured by Seiko Instruments Co. A viscosity was measured by
using an E type viscometer (Type EHD-U manufactured by Tokyo
Vantech Co.) with a rotation number of 0.5 min.sup.-1 (25.degree.
C.). A thixotropic coefficient (hereinafter referred to as TI
value) was shown as a ratio of apparent viscosity at 1 min.sup.-1:
.eta.1 and apparent viscosity at 10 min.sup.-1: .eta.10,
.eta.1/.eta.10.
Example 28
To 30 g of polyether amide imide powder was added 70 g of
.gamma.-butyrolactone followed by stirring. Next, the resultant
mixture was heated at 150.degree. C. for one hour. After heating
was stopped, the mixture was cooled down by allowing to stand to
the room temperature while stirring, to obtain a yellow-brownish
paste. Next, to 100 g (nonvolatile content of 30 g) of the
yellow-brownish paste was added 25 g of silicone rubber filler
(TREFIL E-601 available from Dow Corning Toray Silicone Co., Ltd.)
having an average particle size of 2 .mu.m and the surface thereof
being modified with epoxy groups, and the mixture was mixed,
kneaded and dispersed with three-roll mills to prepare a resin
paste. A semiconductor device was then produced in the same manner
as in Example 1.
Example 29
The resin paste obtained in Example 28 was coated directly onto a
semiconductor substrate of the same kind as in Example 27 by using
a dispense nozzle (an inner diameter of 150 .mu.m) to form a resin
layer. A semiconductor device was then produced in the same manner
as in Example 27.
Example 30
A semiconductor device was produced in the same manner as in
Example 28 except that an amount of the silicone rubber fillers the
surface of which was modified with epoxy groups, used in Example 28
was changed from 25 g to 30 g.
Comparative Example 7
A semiconductor device was produced in the same manner as in
Example 27 except that the polyimide type heat-resistant resin
paste used in Example 27 was solely used.
Comparative Example 8
A semiconductor device was produced in the same manner as in
Example 27 except that the polyimide type heat-resistant resin
paste obtained in Example 27 was suitably blended with silicon
dioxide powders (Aerosil 200 available from Nippon Aerosil Co.) so
that a viscosity of the paste exceeds 1000 Pas, and TI value
exceeds 10.
In Comparative Example 8, the heat-resistant resin paste had a
viscosity of 1200 Pas, and TI value of 10.2.
Comparative Example 9
A semiconductor device was produced in the same manner as in
Example 28 except that the yellow-brownish resin paste obtained in
Example 28 was suitably blended with silicon dioxide powders
(Aerosil 200 available from Nippon Aerosil Co.) so that a viscosity
of the paste exceeds 1000 Pas.
Comparative Example 10
A semiconductor device was produced in the same manner as in
Example 28 except that in stead of using the silicone rubber filler
the surface of which was modified with epoxy groups used in Example
28, acrylic rubber filler having an average particle diameter of 2
.mu.m was used.
Comparative Example 11
A semiconductor device was produced in the same manner as in
Example 28 except that an amount of the silicone rubber filler the
surface of which was modified with epoxy groups used in Example 28
was changed from 25 g to 35 g.
Thus obtained semiconductor devices of Examples 27 to 30 and
Comparative Examples 7 to 11 were, respectively, mounted onto a
substrate (manufactured by Hitachi Chemical Co., Ltd., trade name:
MCL E-67) on which electrodes were formed in the positions
corresponding to the positions of the outer electrodes of the
semiconductor device with a thickness of 1.6 mm and a size of 30
mm.times.30 mm. Then, it was charged in a heat-shock testing
machine and subjected to a heat cycle test of -65.degree. C./15 min
and 150.degree. C./15 min for 1000 cycles. Next, an electric
resistance was measured at the solder connecting portion. Further,
the semiconductor device was polished and failure at the solder
connecting portion was observed and observation of peeling and
crack at the inside of the semiconductor device were carried out.
In Table 5, evaluation results of characteristics of the resin
layers, and further temperature cycle resistance of the
semiconductor device, and evaluation results during the production
process of the semiconductor device prepared in Examples and
Comparative examples are shown.
TABLE-US-00005 TABLE 5 Example Comparative example Item 27 28 29 30
7 8 9 10 11 Modulus -65.degree. C. 1.3 1.2 1.2 0.6 3.4 1.0 3.4 2.9
0.2 of 25.degree. C. 1.0 1.0 1.0 0.5 3.1 0.8 3.1 2.5 0.1 elas-
150.degree. C. 0.7 0.8 0.8 0.3 2.5 0.6 2.5 0.2 0.1 ticity Change in
54 67 67 50 74 60 78 7 50 modulus of elasticity (%) (150.degree.
C./-65.degree. C.) Viscosity 250 530 530 560 380 1200 >1000 540
580 (Pa s) TI value 6.0 4.2 4.2 4.0 3.0 10.2 3.9 3.8 4.2 Glass
transition 220 205 205 200 285 280 240 160 180 temperature
(.degree. C.) 5% weight loss 405 405 405 400 425 420 440 380 395
temperature (.degree. C.) Resin forming Print- Print- Dis- Print-
Print- Print- Print- Print- Print-- method ing ing pense ing ing
ing ing ing ing Resin layer OK OK OK OK OK OK Print- OK OK
formability ing NG Temperature resistant 0/20 0/20 0/20 0/20 5/20
-- -- -- 5/20 cycle test (failure number/tested number)
In Comparative Example 10, a modulus of elasticity was 2.9 GPa at
-65.degree. C. and 0.2 GPa at 150.degree. C., and a changed amount
of the modulus of elasticity was 7%. In addition, a glass
transition temperature was reduced to as low as 160.degree. C., and
there was no sputtering resistant property observed during the
production process of the semiconductor device, whereby it was
impossible to conduct the production process of the second wiring,
leading to inability to obtain a semiconductor device. It can be
understood from Table 5 that, by using a resin for insulating
semiconductor device shown in Examples 27 to 30, tolerance during
the production process of the semiconductor device can be improved
and further, reliability of the semiconductor device itself is
markedly improved.
Example 31
To 233 parts by weight (resin concentration of 30% by weight) of
the polyimide type heat-resistant resin paste (GH-P500 available
from Hitachi Chemical Co., Ltd.) were added 30 parts by weight of
fine particles of silicone rubber elastic material (TREFIL E-601
available from Dow Corning Toray Silicone Co., Ltd.) having an
average particle size of 2 .mu.m and the surface thereof being
modified with epoxy groups and 50 parts by weight of
.gamma.-butyrolactone, and the mixture was mixed and kneaded with
three-roll mills to prepare a heat-resistant resin paste. After the
resulting heat-resistant resin paste was degassed, on a
semiconductor substrate which is a silicon wafer with a diameter of
8 inch and a thickness of 600 .mu.m, on one side of which an
electronic circuit was formed, having the plural number of
electrodes connected to the circuit on the same side, and connected
to the outside on a peripheral part, and on which a polyimide layer
for purpose of protecting the electronic circuit was formed at
least on the surface of the circuit, excluding the electrodes
portion, the resulting heat-resistant resin paste was coated by a
spin coater. This was heat-treated at 80.degree. C. for 15 minutes,
100.degree. C. for 10 minutes, 150.degree. C. for 10 minutes,
200.degree. C. for 15 minutes, and further, 250.degree. C. for 60
minutes to obtain a resin layer.
Then, it was processed so that the electrode portions of the
semiconductor elements are exposed by laser. On the resin layer
surface of the above-mentioned semiconductor substrate, a metallic
sputter layer such as Cr--Cu and Cr--Pd--Cu, etc. is to be formed
with a thickness of 1 to 2 .mu.m, and here, a Cr--Cu layer was
formed with a thickness of 0.5 .mu.m. Then, a plating resist with a
thickness of 10 to 40 .mu.m is to be formed. A thickness of the
plating resist can be selected according to the desired thickness
of an electrolytic Cu plating. Here, a thickness of the resist was
made 20 .mu.m. After exposure, the plating resist was developed,
and electrolytic Cu plating was laminated on the exposed portion of
the sputter metal layer. After plating, the remaining plating
resist was exfoliated to form a second wiring layer. A protective
layer was then formed on the second wiring layer excluding a
mounting part of solder balls. On the electrolytic Cu plating at
which the solder ball (400 .mu.m in diameter) is to be mounted, 0.3
.mu.m of Ni--Au plating layer was formed, then the solder balls are
mounted. Further, the above-mentioned semiconductor substrate was
cut into pieces using a silicon wafer dicing device to obtain a
semiconductor device.
Here, a modulus of elasticity was measured by using a
viscoelasticity analyzer RSAII manufactured by Rheomethoric
Scientific F. E. Co. with a temperature rising rate of 5.degree.
C./min and a frequency of 1 Hz. A glass transition temperature was
measured by using a Thermomechanical analyzer TMA/SS6100
manufactured by Seiko Instruments Co. Modulus of elasticity values
of the employed resins after heat treatment at temperatures of
-65.degree. C., 25.degree. C. and 150.degree. C., a changed ratio
of the modulus of elasticity between -65.degree. C. and 150.degree.
C., and a value of the glass transition temperature are shown in
Table 1.
Example 32
To 30 g of polyether amide imide powder was added 70 g of
.gamma.-butyrolactone followed by stirring. Next, the resultant
mixture was heated at 150.degree. C. for one hour. After heating
was stopped, it was cooled down by allowing to stand to the room
temperature while stirring, to obtain a yellow-brownish paste.
Then, to 100 g (nonvolatile content of 30 g) of the yellow-brownish
paste was added 25 g of silicone rubber filler (TREFIL E-601
available from Dow Corning Toray Silicone Co., Ltd.) having an
average particle size of 2 .mu.m and the surface thereof being
modified with epoxy groups. The mixture was mixed, kneaded and
dispersed with three-roll mills to prepare a resin paste. A
semiconductor device was then produced in the same manner as in
Example 31.
Example 33
The heat-resistant resin paste obtained in Example 31 was coated on
a polytetrafluoroethylene substrate using a bar coater, so that a
thickness after heating and drying becomes 100 .mu.m. This was
heat-treated at 80.degree. C. for 5 minutes, 100.degree. C. for 10
minutes, 150.degree. C. for 10 minutes, and 200.degree. C. for 15
minutes to obtain a film-state resin. The film was laminated on a
semiconductor substrate similar to that used in Example 31,
followed by heat treatment at 250.degree. C. for 60 minutes. A
semiconductor device was then obtained in the same manner as in
Example 31.
Example 34
A semiconductor device was produced in the same manner as in
Example 32 except that an amount of the silicone rubber fillers the
surface of which was modified with epoxy groups used in Example 32
was changed from 25 g to 30 g.
Comparative Example 12
A semiconductor device was produced in the same manner as in
Example 31 except that the polyimide type heat-resistant resin
paste used in Example 31 was used (no fine particles of silicone
rubber elastic material was added).
Comparative Example 13
A semiconductor device was produced in the same manner as in
Example 32 except that instead of using the silicone rubber filler
the surface of which was modified with epoxy groups used in Example
32, acrylic rubber filler having an average particle diameter of 2
.mu.m was used.
Comparative Example 14
A semiconductor device was produced in the same manner as in
Example 32 except that an amount of the silicone rubber filler the
surface of which was modified with epoxy groups, used in Example 32
was changed from 25 g to 35 g.
These semiconductor devices of Examples 31 to 34 and Comparative
Examples 12 to 14 were, respectively, mounted onto a substrate
(manufactured by Hitachi Chemical Co., Ltd., trade name: MCL E-67)
on which electrodes were formed in the positions corresponding to
the positions of the outer electrodes of the semiconductor device
with a thickness of 1.6 mm and a size of 30 mm.times.30 mm. Next,
it was charged in a heat-shock testing machine and subjected to a
heat cycle test of -65.degree. C./15 minutes, and 150.degree. C./15
minutes for 1000 cycles. Next, an electric resistance was measured
at the solder connecting portion. Further, the semiconductor device
was polished and failure at the solder connecting portion was
observed, and observation of peeling and crack at the inside of the
semiconductor device were carried out. The results are shown in
Table 6.
TABLE-US-00006 TABLE 6 Comparative Example example Item 31 32 33 34
12 13 14 Modulus -65.degree. C. 1.3 1.2 1.3 0.6 3.4 2.9 0.2 of
25.degree. C. 1.0 1.0 1.0 0.5 3.1 2.5 0.1 elas- 150.degree. C. 0.7
0.8 0.7 0.3 2.5 0.2 0.1 ticity Change in 54 67 54 50 74 7 50
modulus of elasticity (%) (150.degree. C./-65.degree. C.) Glass
transition 220 205 220 200 285 160 180 temperature (.degree. C.)
Resin forming Spin Spin Lami- Spin Spin Spin Spin method coating
coating nate coating coating coating coating Resin layer OK OK OK
OK OK -- OK formability Temperature resistant 0/20 0/20 0/20 0/20
5/20 -- 5/20 cycle test (failure number/tested number)
In Comparative Example 13, the modulus of elasticity was 2.9 GPa at
-65.degree. C. and 0.2 GPa at 150.degree. C., and a changed amount
of the modulus of elasticity was 7%. Moreover, a glass transition
temperature was reduced to as low as 160.degree. C., and there was
no sputtering resistance property during the production process of
the semiconductor device, whereby it was impossible to conduct the
production process of the second wiring layer, leading to inability
of obtaining a semiconductor device.
On the contrary, it can be understood that, by using a resin shown
in Examples 31 to 34, resistance during the production process of
the semiconductor device can be improved and further, reliability
of the semiconductor device itself is markedly improved.
Example 35
Using FIG. 1, one example of the present invention is
explained.
To 233 parts by weight of the polyimide type heat-resistant resin
paste (GH-P500 available from Hitachi Chemical Co., Ltd.) were
added 30 parts by weight of fine particles of silicone rubber
elastic material (TREFIL E-601 available from Dow Corning Toray
Silicone Co., Ltd.) having an average particle size of 2 .mu.m and
the surface thereof being modified with epoxy groups and 50 parts
by weight of .gamma.-butyrolactone, and the mixture was mixed and
kneaded with three-roll mills and degassed to prepare a
heat-resistant resin paste. The heat-resistant resin paste was
coated on a polytetrafluoroethylene substrate using a bar coater,
so that a thickness after heating and drying becomes 25 .mu.m. This
was subjected to heat-treatment at 80.degree. C. for 5 minutes,
100.degree. C. for 10 minutes, 150.degree. C. for 10 minutes, and
200.degree. C. for 15 minutes and further, 250.degree. C. for 60
minutes to obtain a resin film. A modulus of elasticity of the
resin film was measured by using a viscoelasticity analyzer RSAII
manufactured by Rheometric Scientific F. E. Co., with a temperature
rising rate of 5.degree. C./min, and a frequency of 1 Hz.
On a semiconductor wafer 3 with a diameter of 8 inch and a
thickness of 600 .mu.m, on which an electronic circuit was formed,
the heat-resistant resin paste was printed by using a screen
printer (LS-34GX attached with an alignment device manufactured by
New Long Seimitsu Kogyo K.K.) and a metal mask (manufactured by
Mesh Kogyo Co., thickness: 100 .mu.m). The printed portion is the
same as an outer shape of the semiconductor device and is a range
excluding the dicing area 8. This was heat-treated at 80.degree. C.
for 5 minutes, 100.degree. C. for 10 minutes, 150.degree. C. for 10
minutes, 200.degree. C. for 15 minutes, and further, 250.degree. C.
for 60 minutes to obtain a resin layer 1 (FIG. 1(b)).
Then, it was processed by laser with a diameter of 50 .mu.m until
the electrode pad 5 is exposed at the desired position of the resin
layer 1 (FIG. 1(c)).
On the upper surface of he resin layer 1, a sputter metal film of
Cr was formed with a thickness of 0.5 .mu.m by using a sputtering
apparatus, a plate resist layer was coated on the sputter metal
layer with a thickness of 20 .mu.m, a plate resist layer was formed
by exposure and developing treatment at which a Cu plate wiring is
to be formed, after reaching the Cu wiring to 15 .mu.m, the plate
resist was peeled off, and further, the portion at which the
sputter metal film had been exposed was removed to form a second
wiring layer 6 (FIG. 1(d)).
On the resin layer 1 at which the second wiring layer 6 had been
formed, the above-mentioned heat-resistant resin paste was printed
by using a screen printing machine (manufactured by New Long
Seimitsu Kogyo, K.K., LS-34GX attached with an alignment apparatus)
and a metal mask (manufactured by Mesh Kogyo K.K., thickness: 40
.mu.m) so that the thickness after heating and drying becomes 20
.mu.m. The printed portion is the same as an outer shape of the
semiconductor device and a range excluding the dicing area 8. This
was subjected to heat treatment at 80.degree. C. for 5 minutes,
100.degree. C. for 10 minutes, 150.degree. C. for 10 minutes,
200.degree. C. for 15 minutes, and further, 250.degree. C. for 60
minutes to obtain a protective layer 2 of the second wiring layer
(FIG. 1(e)).
At the desired position of the protective layer of the second
wiring layer, processing was carried out until the second wiring
layer 6 was exposed by laser with a diameter of 300 .mu.m to obtain
an outer connection terminal 7 (FIG. 1(f)).
The semiconductor wafer 3 was cut at the dicing area 8 to form the
respective semiconductor devices (FIG. 1(g)).
At the outer connection terminal 7 of the semiconductor device,
solder ball with a diameter of 0.40 mm was mounted, and then, the
semiconductor device was mounted on a substrate (manufactured by
Hitachi Chemical Co., Ltd., trade name: MCL E-67) on which
electrodes had been formed at the positions corresponding to the
outer electrode terminals of a semiconductor device having a size
of 30 mm.times.30 mm and a thickness of 1.6 mm. This product was
placed in a thermal shock testing machine and a temperature cycle
test were carried out 1000 cycles wherein -65.degree. C. for 15
minutes and 150.degree. C. for 15 minutes is one cycle.
Example 36
To 30 g of polyether amide imide powder was added 70 g of
.gamma.-butyrolactone and the mixture was stirred. Next, the
mixture was heated at 150.degree. C. for one hour. After stopping
the heating, the mixture was naturally cooled by allowing to stand
to room temperature under stirring to obtain a yellow-brownish
paste. Then, to 100 g (nonvolatile component: 30 g) of the
yellow-brownish paste was added 25 g of a silicone rubber filler
(TREFIL E-601 available from Dow Corning Toray Silicone Co., Ltd.)
having an average particle size of 2 .mu.m and the surface of which
was modified by epoxy groups, and the mixture was mixed, kneaded
and dispersed by the three-roll mixer to obtain a resin paste. A
semiconductor device was then obtained in the same manner as in
Example 35.
Example 37
A semiconductor device was obtained in the same manner as in
Example 36 except for changing an amount of the silicone rubber
filler the surface of which was modified by epoxy groups from 25 g
to 30 g.
Comparative Example 15
A semiconductor device was prepared in the same manner as in
Example 35 except for using the polyimide type heat-resistant resin
paste of Example 35.
Comparative Example 16
A semiconductor device was prepared in the same manner as in
Example 36 except for using an acryl rubber filler having an
average particle size of 2 .mu.m in place of the silicone rubber
filler the surface of which had been modified by epoxy groups of
Example 36.
Comparative Example 17
A semiconductor device was prepared in the same manner as in
Example 36 except for changing the amount of the silicone rubber
filler the surface of which had been modified by epoxy groups from
25 g to 35 g of Example 36.
With regard to the thus obtained semiconductor devices of Examples
35 to 37 and Comparative Examples 15 to 17, modulus of
elasticities, glass transition temperatures, temperature cycle
tests and resin layer formability were evaluated or measured.
Further, when failure occurred, the semiconductor device was
polished and exfoliation and crack at the solder connecting portion
or inside of the semiconductor device were observed. The results
are shown in Table 7. As a result, in Examples 35 to 37, no failure
at the solder connecting portion nor exfoliation or crack at the
inside of the semiconductor device was observed by 1000 cycles.
TABLE-US-00007 TABLE 7 Example Comparative example Item 35 36 37 15
16 17 Modulus of 1.0 1.0 1.0 3.1 2.5 0.1 elasticity (GPa,
25.degree. C.) 5% weight loss 405 405 405 425 420 395 temperature
(.degree. C.) Glass transition 220 220 220 285 160 180 temperature
(.degree. C.) Resin layer OK OK OK OK -- OK formability Temperature
resistant 0/20 0/20 0/20 5/20 -- 5/20 cycle test (failure
number/tested number) Failure -- -- -- Solder -- Break- position
connect- age of ing wiring portion
In Comparative Example 16, a glass transition temperature was
reduced to as low as 160.degree. C., and there was no sputtering
resistance property during the production process of the
semiconductor device, whereby it was impossible to conduct the
production process of the second wiring layer, leading to inability
to obtain a semiconductor device. From Table 7, by using the resin
layer of Examples 35 to 37, resistance during the production
process of the semiconductor device can be improved and further,
reliability of the semiconductor device itself is markedly
improved.
Utilizability in Industry
According to the resin composition of the present invention, a
coated film having the same resin characteristics as in the
polyimide, i.e., high strength and excellent in flexibility can be
obtained without imidation step. Moreover, it is possible to form a
precise pattern by screen printing or dispense coating, etc., so
that a semiconductor device using the resin composition of the
present invention gives good characteristics.
The heat-resistant resin paste of the present invention can be
widely utilized for a coating material, an adhesive, a stress
relaxing material of a semiconductor device, etc., a modulus of
elasticity of which can be optionally controlled and capable of
forming a resin film excellent in heat resistance. Also, it has
thixotropic property and can be applied to a coating system
excellent in coating efficiency such as screen printing or
dispense.
The semiconductor device of the present invention has a resin film
obtained from a heat-resistant resin paste which has a thixotropic
property, and can be widely utilized for a coating material, an
adhesive, a stress relaxing material of a semiconductor device,
etc., elasticity of which can be optionally controlled and capable
of forming a resin film excellent in heat resistance.
According to the present invention, the resin layer is low
elasticity so that a stress applied to an outer electrode terminal
after packaging can be well relaxed and has heat-resistance so that
resistance at the step of forming a second wiring layer by
sputtering is excellent. Moreover, it is excellent in solvent
resistance at the step of forming a second wiring layer by plating.
Furthermore, by using the resin having the above-mentioned
characteristics, a semiconductor device excellent in reliability
can be obtained without using an underfill resin.
The present invention further provides a method of producing a
semiconductor device excellent in adhesiveness between the resin
layer and the wiring protecting layer, and semiconductor devices
excellent in packaging reliability can be integrally formed on a
semiconductor wafer.
* * * * *